Rancagua Bishop Alejandro Goic presented his resignation as head of the Bishops' Conference sex abuse prevention board, the latest episode in a Chilean abuse scandal which has rocked Pope Francis's papacy.
The church accepted Goic's immediate resignation from the board set up in 2011 to investigate sexual abuse by clergy, following the case of Chilean priest Fernando Karadima.
He was accused of child molestation in the 1980s and 1990s.
Karadima was suspended for life by the Vatican, but several members of the Chilean church hierarchy are accused by victims of ignoring and covering up Karadima's abuse.
Seven years later, yet another wide-ranging abuse case has emerged.
Nicknamed "the Family," 13 priests and a deacon from Rancagua were accused by churchgoer Elisa Fernandez of sex abuse and lavish spending of church funds. She made her allegations on Channel 13 last week.
Goic, 78, told local media he needed to resign to focus on shedding light on the charges against the fourteen, who have been defrocked.
A priest said in the Channel 13 report that the group formed a sex abuse ring a decade ago, and engaged in sex acts with no regard for whether or not the victims were minors.
In addition, offenders used social media to control their interactions with victims and used church money for trips abroad as well as expensive car services with young friends, the report added.
Last week, 34 Chilean bishops announced their resignation over child sex abuse in the church, after Pope Francis summoned them.
Argentine-born Francis has said it must not happen again on his watch, but Francis himself became caught up in the tragedies when he defended Chilean bishop Juan Barros who was accused of covering up Karadima's wrongdoing.
Francis has apologized to the victims, three of whom he received at the Vatican, and admitted he had made "grave mistakes" after reading a 2,300-page report on abuses in Chile.
Since 2000, about 80 Roman Catholic priests have been reported to authorities in Chile for alleged sexual abuse.
Some analysts note that Chile's long tradition of having the church not subject to civilian law lent itself to impunity and cover-ups
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