We describe a simple, efficient, and environmentally benign strategy for the hydrotrifluoromethylation of unactivated alkenes and alkynes through a radical-mediated reaction using an inorganic electride, [Ca2N]+·e-, as the electron source. In the transformation, anionic electrons are transferred from [Ca2N]+·e- electrides to the trifluoromethylating reagent CF3I to initiate radical-mediated trifluoromethylation. This methodology, without need for a transition-metal catalyst, allows access to diverse hydrotrifluoromethylated and iodotrifluoromethylated products in a short reaction time. In addition, iodotrifluoromethylation of alkynes proceeds selectively upon the control of electride amount.

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