A series of platinum complexes featuring phosphine and isocyanide ligands [PtX 2(PPh 3)(CNCy)] (X = Cl, Br, and I) as well as their parent phosphine [PtX 2(PPh 3) 2] and isocyanide [PtX 2(CNCy) 2] analogues have been prepared and evaluated as catalysts for the photocatalytic hydrosilylation of alkynes. Under violet light irradiation (λ max = 400 nm), phosphine-isocyanides complexes [PtX 2(PPh 3)(CNCy)] gave high yields of silylated products (product yield up to 99%, TONs up to 1.98 × 10 3). The blue light irradiation (λ max = 450 nm) was more suitable for the parent phosphine complexes [PtX 2(PPh 3) 2], which showed comparable efficiency (product yield up to 99%, TON up to 1.98 × 10 3), while isocyanide complexes [PtX 2(CNCy) 2] were not active.