But he continued to perform healings at well-attended public ceremonies that brought him a following in Europe.
Archbishop Emmanuel Milingo, the former head of the Roman Catholic Church in Zambia, married 43-year-old doctor, Maria Sung - whom he had never met before - during a collective wedding ceremony organised by the Moonies in New York.
Monsignor Milingo defended himself by pointing out that exorcism and healing was carried out by Jesus Christ himself.
The 71-year-old former archbishop of Lusaka married Ms Sung on Sunday in a Unification Church (commonly known as the Moonies) ceremony, attended by 60 couples.
'Lifetime of devotion'
Roman Catholic Church spokesman Joaquin Navarro Valls, said: "By joining a public wedding ceremony celebrated by the 'Moon' sect he has placed himself outside the Catholic Church and seriously damaged the link between bishops and the Church."
"After a lifetime of devotion to the Church and to my priestly vows, the Lord has called me to take a step that will change my life forever," he said in a statement before the ceremony.
The maverick Catholic was archbishop of Lusaka, Zambia, until 1983, when he resigned under pressure from Rome - an almost unprecedented event.
Original sin
The Vatican objected to allegations that he carried out faith healings and exorcisms and moved him to Rome to make it easier to keep an eye on him.
But he continued to perform healings at well-attended public ceremonies that brought him a following in Europe.
Last year, the Vatican issued new guidelines on exorcism that were widely understood to be aimed at Monsignor Milingo.
He was quietly retired from his position at the Pontifical Council for Pastoral Care of Migrants and Itinerant People last year.
He has appeared at group weddings conducted by the Rev Moon in the past two years.
Monsignor Milingo said he and his wife would move to Africa.
The Rev Moon personally arranges many of the pairings at the mass weddings that are a central part of the church he leads.
The 81-year-old founded the Unification Church in 1954 as a movement dedicated to building world peace through loving families.
His philosophy is based on the original sin - the temptation of Eve by Satan and the ensuing downfall of mankind.
Followers believe that the Messiah was sent by God to rid the human race of this sin and start anew. But the objective was never fulfilled because Christ was crucified before he could marry.
The Reverend Moon sees his mission as continuing the work of Jesus Christ in creating a new "family of man" and in 1992 he declared that he and his wife were the true parents of all humanity.