Comprehensive SummaryHere, we demonstrate a readily prepared anthrazoline photocatalyst, which can effectively promote C—O bond formation reactions with the aid of Ni(II) complex. This methodology enables the esterification (36 examples) and etherification (8 examples) with a broad range of scope, allowing aryl and alkyl halides coupled with diverse carboxylic acids/alcohols. Our metal‐free photocatalysts have a potential broad application, may serve as an alternative to some iridium and ruthenium based photocatalysts, and are of potential importance to the pharmaceutical industry.