Platinum(II) metalla‐N‐heterocyclic carbene complexes featuring pyridyl heterocyclic moiety demonstrate remarkable catalytic efficiency in alkyne hydrosilylation under green light irradiation. The photocatalytic properties of complexes are rationalised by the photo‐induced charge transfer occurring in extended condensed system identified with the help of various experimental (UV/vis and emission spectroscopy, cyclic voltammetry) and theoretical methods (DFT/TD‐DFT, IFCT analysis).