Homometallic copper complexes with alkenylidene ligands are discussed as intermediates in catalysis but the isolation of such complexes has remained elusive. Herein, we report the structural characterization of copper complexes with bridging and terminal alkenylidene ligands. The compounds were obtained by irradiation of Cu(I) complexes with N-heterocyclic diazoolefins ligands. The complex with a terminal alkenylidene ligand required isolation in a crystalline matrix, and its structural characterization was enabled by in crystallo photolysis at low temperature.