The photoredox/Ni dual catalysis is an appealing strategy to enable unconventional C-heteroatom bond formation. While significant advances have been achieved using this system, intermolecular C-(sp(3))-N bond formation has been relatively underdeveloped due to the difficulty in C-(sp(3))-N reductive elimination. Herein, we present a new mechanistic approach that utilizes dioxazolones as the Ni-(II)-nitrenoid precursor to capture carbon-centered radicals by merging proton-coupled electron transfer (PCET) with nickel catalysis, thus forming synthetically versatile N-alkyl amides using alcohols. Based on mechanistic investigations, the involvement of (kappa(2)-N,O)-Ni-(II)-nitrenoid species was proposed to capture photoredox PCET-induced alkyl radicals, thereby playing a pivotal role to enable the C-(sp(3))-N bond formation.