Pope Benedict XVI has excommunicated a Zambian archbishop, Emmanuel Milingo, two days after he ordained four married men as bishops.
Milingo married a South Korean woman at a mass wedding
A Vatican statement said he had been automatically excommunicated under church law because of his actions.
Archbishop Milingo, 76, who now lives in the US, performed the ordination ceremony in Washington DC on Sunday.
The Catholic diocese in Washington immediately declared the installations to be invalid.
Correspondents say that Archbishop Milingo has long been a controversial figure in the Roman Catholic Church.
Six years ago, he married a South Korean woman at a mass wedding in New York organised by the Korean-based Unification Church - the so-called "Moonies".
He was later persuaded by the Vatican to renounce the marriage, but has since rejoined his wife.
The Zambian preacher was nominated archbishop of Lusaka at age 39, a post he held for 14 years before a disagreement with the Vatican over his activities as a healer and an exorcist.
He was recalled to Rome in 1983 but managed to keep his rank of archbishop.
Archbishop Milingo then gained a strong following in a Church where he had been stationed near Rome because of his reputation as an exorcist.
But Catholic officials accused him of promoting African indigenous beliefs by performing mass exorcisms and healing ceremonies.
Mr Milingo announced earlier this year that his new mission was to persuade the Church to allow priests to marry.
"The Holy See has patiently witnessed the evolution of the events which, unfortunately, have led Archbishop Milingo to a state of irregularity and progressive open break from communion with the Church," the Vatican said in a statement.
The Vatican statement cited his "attempted marriage" and Sunday's ordinations.
The four married men he ordained on Sunday were also automatically excommunicated, it said.