Reported herein is an ovel visible-light photoredox system with Pd(PPh 3 ) 4 as the sole catalyst for the realization of the first direct cross-coupling of C(sp 3 )ÀHb onds in N-aryl tetrahydroisoquinolines with unactivated alkyl bromides. Moreover,i ntra-and intermolecular alkylations of heteroarenes were also developed under mild reaction conditions.A variety of tertiary,s econdary,a nd primary alkylb romides undergo reaction to generate C(sp 3 )ÀC(sp 3 )and C(sp 2 )ÀC(sp 3 ) bonds in moderate to excellent yields.T hese redox-neutral reactions feature broad substrate scope (> 60 examples), good functional-group tolerance,and facile generation of quaternary centers.Mechanistic studies indicate that the simple palladium complex acts as the visible-light photocatalyst and radicals are involved in the process. Scheme 1. Visible-light photocatalysis.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.