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Chiu said the accord followed a trial where the court found Walgreens substantially contributed to the epidemic and created a public nuisance.
U.S. District Judge Charles Breyer had ruled last August that the drugstore chain failed to properly investigate suspicious opioid orders for nearly 15 years.
Walgreens had been the only remaining defendant, after several drugmakers and distributors had settled with the city.
San Francisco subsequently estimated it might cost $8.1 billion to abate the opioid crisis, and said Walgreens was legally liable for the entire amount.
Walgreens did not immediately respond on Wednesday to a request for comment. It had previously denied liability.
