Basic amines show broad bioactivity and remain a promising source of new medicines. The direct photoalkylation of imines offers a promising strategy for complex amines. However, the lack of efficient imine photoreactivity hinders this reaction and remains a fundamental limitation in organic photochemistry. We report an efficient photoalkylation of imines that provides primary amines directly without protecting or leaving groups. The transformation effects C-H addition across N-H imines under energy-transfer photocatalysis by a ketone. Our method is distinguished from organometallic, metal-catalyzed, and photoredox approaches to imine alkylation by its lack of protecting groups and its broad scope, which includes unactivated alkanes, protic substrates, basic amines, heterocycles, and ketone imines. We highlight this scope through the condensation and alkylation of two pharmaceutical ketones, providing complex amines succinctly. Our mechanistic analysis supports a three-step process, involving hydrogen-atom transfer to an imine triplet excited state, intersystem crossing, and radical recombination, with photocatalytic enhancement through energy transfer. We further show that N-H imines are more photoreactive than N-substituted imines, a distinction partially explained by sterics and side reactions. To fully explain this distinction, we introduce the thermodynamic parameter excited-state hydrogen-atom affinity, which is highly effective at predicting the photoreactivity of imines.