Williams is charged with 23 federal counts, including bribery and corruption.
Wolf issued a statement on Friday saying:
"While District Attorney Williams, like any defendant, is entitled to the presumption of innocence, it is clear that his focus should be on his defense and it is beyond time for him to step down immediately from his post as District Attorney.
The people of Philadelphia need a district attorney fully focused on, and legally capable of, executing the important duties of the top law enforcement official in Pennsylvania's largest city. His resignation will allow the employees of the office to focus on their work and help the citizens they serve move on."
Williams agreed to have his law license temporarily suspended.
He could go to trial by the end of May.
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