The photolysis of mixed ligand complexes of the type MLn(N3)2 (M=Ni, Pd, Pt; L = phosphane and diphosphane ligands, respectively; n = 1, 2) was monitored by electronic spectroscopy in absorption, emission and excitation. Initial quantum yields of these complexes were measured in CH2Cl2 and EtOH in dependence on the irradiation wavelength. Photochemically formed MOIn fragments of Pd and Pt are distinguished by an intensive emission detected at 77 K. No emission was observed with respect to the appropriate NiO fragments. An initial emission at 615 nm detected by irradiating Pd(PPh3)2(N3)2 at 77 K is explained by assuming a photochemical cis/trans isomerization Quenching experiments have been performed by using Ru(bpy)3Cl2, Os(bpy)3Cl2, Re(CO)3(phen)Cl and Cr(bpy)3(ClO4)3 as sensitizers and the mixed-ligand complexes under discussion as quenchers.