This work describes a strategy to utilise uranyl for direct alkynylation and olefination of amides. The uranyl cation (UO₂²⁺) has been identified as a highly oxidizing agent to abstract hydrogen atoms from C–H bonds for the formation of carbon-centered radicals. The photoexcitation of uranyl cations provides a range of carbon-centered radicals via hydrogen atom transfer, which can be successfully applied in cross-coupling reactions with a broad range of alkynyl and alkenyl bromides.