A palladium-catalyzed β-C(sp³)–H nitrooxylation of aliphatic alcohols with AgNO₂ is reported. An 8-formylquinoline-derived oxime is installed as an exo-type directing group for sp³ C–H activation and selectfluor acts as the oxidant. The reaction tolerates a variety of functional groups and shows good selectivity for β-C–H nitrooxylation of alcohols.