Rozen

Well, this dude was never revealed in any way, even the dolls who calls him Father don't remember him being physical. He's just the person who created the dolls so he could find this so-called Alice and made them fight each other. Which is why I write about him last and I hate his very existence but if it weren't for him, the adorable dolls won't have existed either..

Father appears to have acquired immortality through alchemy, and was forced to go by many aliases throughout time, such as the Count of St. Germain. He has spoken to Shinku various times (but not in person) and indicated that besides battling, there is another way to end the Alice Game ..which was also never revealed in any way.

Enju

He was initially believed to be Rozen himself, but is merely Rozen's jealous apprentice. Enju was obsessed with surpassing Rozen as the greatest dollmaker; to achieve that end, he created Barasuishou to oppose the Rozen Maidens, take their Rosae Mysticae, and finish as the last doll standing.

Though occasionally bitter, Enju takes his art very seriously; he even gives brief words of reassurance to halfway finished creations. Enju also somewhat bears a resemblance to Rozen

Laplace no ma   Laplace no Ma

The demon of Laplace. He appears as an anthropomorphous white rabbit in a tuxedo and a top hat. He is neither sinister nor kind, and tends to speak in riddles. His brief appearances in the N-Field leave the Rozen Maidens with nothing more than poetic and seemingly nonsensical advice. Despite seeming to support Barasuishou against the Rozen Maidens, and is seen dancing with Kirakishou at the end, Laplace no Ma's true motives remain a mystery. Laplace is a very clear reference to Rozen Maiden's inspiration taken from Alice in Wonderland, with appearance and personality deriving from both the white rabbit and the Cheshire cat.

It is revealed that he has been in Enju's company since before Shinku and Suigintou's rivalry began, and was searching for Rozen Maidens even then, though it is not said why.

Kakizaki Megu

Megu is a sickly girl (she suffers from a congenital heart disease) who is Suigintou's medium. She lives in a hospital room, under constant care from nurses. Megu has a very bleak outlook on life and often prays for an 'Angel of Death' to take her away. She sees herself as a burden upon her parents, who she claims are 'guilty' of having her. She initially believes that Suigintou is the Angel of Death she has hoped for and requests that Suigintou kill her by draining away her energy. Despite her apathy and, at times, contempt towards life in general, she is quite needy, and increasingly desires Suigintou's company, even throwing tantrums when Suigintou is away. Megu's blatant disrespect towards her father is shocking to Suigintou, who would never consider such an attitude toward her own Father.

Kashiwaba Tomoe

An honor student at Jun's school. She is quiet, and kind-hearted, although her speech and style tend to be very dry and she will often hide her true feelings. Tomoe was originally Hinaichigo's medium, but the bond between them was broken when Hinaichigo relied too much on Tomoe's energy and was defeated by Shinku. Currently, Tomoe helps Jun in his dealings with the Rozen Maidens and also assists him with his make-up work for school. Before it was severed, Tomoe's bond with Hinaichigo was about as close as siblings.

Tomoe learned kendo from her father from an early age and is a member of the kendo club at school. She is often seen carrying her shinai when class is over. She is also a member of the school committee, seemingly reluctantly.

Sakurada Nori

Jun's older sister. An avid lacrosse player, who had to give up many of her other hobbies when she took care of Jun while their parents are out of the country on business. While initially resistant to the responsibility, Nori became kind and gentle towards Jun. She unfortunately takes the brunt of Jun's abuse and criticism. Shinku constantly provides Nori with advice on everything from the proper way to brew tea, to taking care of Jun. Nori is very fond of the dolls who live and play in her house.

Although generally she is kind, gentle and accepts all the criticism from Jun, it is agreed by the dolls that she's the worst when she's angry.

He spends a lot of time in front of his computer, and has a hobby of ordering things from the Internet — mostly fake magical or occultic implements— and then returning them before he has to pay, for the thrill of receiving something ridiculously stupid. He is also interested in cars and collects miniature versions of them. When he comes into possession of Shinku and winds her up, he is unwittingly and unwillingly caught in the crossfire of the Alice Game — Shinku declares him to be her "servant" and demands that he obey her at all times. Jun is extremely skilled at crafts and at sewing. Although he is arrogant, and occasionally cold and rude, he cares for others but typically refuses to let his feelings show. He is especially friendly with Hinaichigo, and at times, blushes around Shinku, which betrays that he cares deeply for her.

Initially he was a 'hikikomori', a Japanese term for people who choose to withdraw from the society due to some embarrassment that had traumatized them. In Jun's case, this was never clearly stated.. or I just wasn't paying that much attention to the humans in this anime.. hahaha..! So, anyways.. However, as time passes and he spends a lot of it with the dolls, Jun finally succeeds in pulling out of his own safe world and continue going to school. (oh, yeah. He didn't go to school after whatever it was that happened)

Jun is Shinku's medium, and later in the story he also sworn allegiance to Suiseiseki, given the circumstances, shit they were in at that time. Four of the six dolls (Suiseiseki, Souseiseki, Shinku and Hinaichigo) takes residence in his house.