Perfluoroalkyl compounds are persistent environmental pollutants due to their chemical and thermal stability. Hydrodefluorination is one of the most promising strategies for the disposal of fluorine-containing compounds, which has attracted much attention from a broad spectrum of scientific communities. Herein, we disclose a metal-free, visible-light-promoted protocol for the exhaustive hydrodefluorination of a wide variety of trifluoromethylarenes with up to 95% yields. Moreover, methyl-d3 groups can be obtained via deuterium water with a D ratio of up to 94%.