A selective green-light-induced hydroselenation of alkenes with diselenides using Hantzsch ester as the hydrogen donor has been developed. In the case of electron-neutral diaryl diselenides and diacyl ones, alkenes undergo anti-Markovnikov-selective hydroselenation. When switching to electron-deficient diaryl diselenides and dialkyl ones, Markovnikov-selective hydroselenation occurs.