A direct defluorinative multifluoroarylation of unactivated sp3 C-H bonds through hydrogen atom transfer using photoredox catalysis has been developed. The C(sp3)-C(sp2) couplings between C(sp2)-F bonds and corresponding C(sp3)-H bonds adjacent to heteroatoms proceeded smoothly to afford the desired products in moderate to good yields. Preliminary mechanistic investigations on this novel transformation revealed that the C-H cleavage process might be involved in the rate-determining step.