We present the synthesis and photophysical properties of six novel N-phenyl-1,3-thiazol-2-ylidene platinum(II) complexes with sterically demanding N-aryl-βketoiminate ligands. Diverse aryl substituents at the coordinating nitrogen atom (phenyl, mesityl, 2,6-diisopropylphenyl, 4cyanophenyl, 1-naphthyl, and 2,4-difluorophenyl) of the Naryl-(3Z)-4-amino-3-penten-2-ones exclusively yielded the SP-4-3 coordinated C ∧ C* cyclometalated platinum(II) complexes as single isomers as a consequence of the low steric demand of the C ∧ C* cyclometalating thiazole ligand and the bulkiness of the β-ketoiminate ligands. The formation of this isomer was confirmed by 195 Pt NMR and extensive 2D NMR experiments, two solid-state structures, and the results of DFT calculations. As a proof of principle, two complexes with the sterically less demanding β-ketoiminate ligands (3Z)-4-amino-3-penten-2-onato and (2Z)-3-amino-1-phenyl-2-buten-1-onato were synthesized and isolated as an isomeric mixture.