The issue has historically troubled the Church, with many opposing the appointment of females.
The commission of seven men and six women will study the issue, and look into the historical role of women in the early years of the Church.
Deacons are a clergy rank one below priest.
They are ordained ministers who can preach or preside over weddings and funerals, but cannot celebrate Mass.
Supporters say women are poorly represented within the church and that appointing female deacons would give women greater sway in decision-making.
The Pope first remarked in May that he was willing to set up a commission to study the issue.
He had told senior members of women's religious orders he was open to the issue of considering female deacons: "It would be useful for the Church to clarify this question. I agree.'"
The Vatican also clarified that the Pope was not considering the possibility of ordaining women priests.
Currently all Catholic priests and deacons are male. Priests must be celibate, but deacons can be married men.
It was two years ago, addressing a meeting of international Catholic theologians, including both men and women, that Pope Francis first raised the possibility of opening up more posts to women inside his Church.
He said "women are the strawberry on the cake and there is need for more of them".
The remark, with its perhaps unintended overtones of male chauvinism, was taken as demeaning by some Catholic women. But now the Pope has appointed 13 leading theologians from various parts of the world to look into the historical role of women in the early years of the Church.
Pope Francis's immediate predecessors declared that women could never be ordained as priests, but now a new chink appears to have opened in the protective armour of the Roman Catholic Church's all-male and all-celibate clergy.
Pope Francis has set up a special commission to study whether women will be allowed to become deacons in the Catholic Church.