The ability to selectively forge C–heteroatom bonds via C–F scission is typically accomplished by metal catalysts, specialized ligands and/or harsh conditions. Herein, we describe a base‐mediated defluorosilylation of unactivated sp2 and sp3 C–F bonds that obviates the need for metal catalysts. This protocol is characterized by its simplicity, mild conditions and wide scope, even within the context of late‐stage functionalization, constituting a complementary approach to existing C–Si bond‐forming protocols.