Hydrofunctionalization of alkenes represents a fundamental strategy in synthetic organic chemistry. Herein, we describe a visible-light-promoted approach for the anti-Markovnikov hydrooxygenation of unactivated alkenes. Our protocol features the utilization of a cost-effective, bench-stable, and easy-to-handle oxime ester as the reagent, enabled by energy-transfer catalysis. This methodology exhibits excellent functional group tolerance and mild reaction conditions, rendering it suitable for the hydroesterification of pharmaceutically relevant molecule-derived alkenes.