Herein we report a highly selective photoredox C(sp3)?H alkylation/arylation of ethers through the combination of a photo‐organocatalyst (benzaldehyde) and a transition‐metal catalyst (nickel). This method provides a simple and general strategy for the C(sp3)?H alkylation/arylation of ethers. A selective late‐stage modification of (?)‐ambroxide has also been conducted to demonstrate the applicability of the method.