Herein we disclose a catalytic synthesis of cycloalkanols that harnesses the potential of N₂O as an oxygen transfer agent onto sp³-hybridized carbons. The protocol is distinguished by its mild conditions and wide substrate scope, thus offering an opportunity to access carbocyclic compounds from simple precursors even in an enantioselective manner. Preliminary mechanistic studies suggest that the oxygen insertion event occurs at an alkylnickel species and that N₂O is the O transfer reagent.