Copper(I) N-heterocyclic carbene (CuNHC) complexes are more catalytically active than traditional transition metal salts for the cyclopropenation of internal alkynylsilanes and diazoacetate compounds. A series of 1,2,3-trisubstituted and 1,2,3,3-tetrasubstituted cyclopropenylsilane compounds were isolated in good overall yields. An interesting regioselective and chemodivergent reaction pathway was also observed to furnish a tetra-substituted furan for an electron-rich donor/acceptor diazoacetate. Finally, a practical synthesis of a cyclopropenyl-containing starting material that is useful for bioorthogonal chemistry is also described.