AbstractA synthetic route leading to bis‐heteroleptic cyclometalated complexes magnified image is described. The complexes [2‐(2′‐thienyl)pyridinato‐N, C‐3′]{2‐[3′‐(trimethylsilyl)2′‐thienyl]pyridinato‐N, C3′}platinum(II) ([Pt(thpy) (TMS‐thpy)]; I) and (l‐phenylpyrazolato‐N2, C2′)[2‐(2′‐thienyl)pyridinato‐N, C3′]platinum ([Pt(Phpz)(thpy)]; II) are characterized by UV/VIS, NMR, and mass spectroscopy. Thermal and photochemical oxidative addition reactions yield two out of the 10 possible pairs of enantiomers of octahedral Pt(IV) compounds.