A convenient and general strategy for the synthesis of stable bis(cyclometalated) pentafluorophenyl PtIV complexes fac‐[Pt(C^N)2(C6F5)Cl] (3 a–f) and mer‐[Pt(C^N)2(C6F5)(CN)] (4 c,d) has been developed. Complexes 3 were selectively generated by low‐temperature oxidation of the cyclometalated PtII complexes [Pt(C^N)(HC^N)(C6F5)] 2 [prepared from cis‐[Pt(C6F5)2(HC^N)2] (1) intermediates] with PhICl2 and subsequent metalation of the pendant HC^N ligand. Complexes 3 a,b were also alternatively generated by irradiation (Hg lamp, 400 W) of complexes 2 a,b, respectively, in CH2Cl2. This latter reaction proceeds via the hydride PtIV species cis‐[Pt(C^N)2(C6F5)H], detected as the only intermediate species. The molecular structures of 1 a,d, 2 a, and 3 a,b,d,e were confirmed by X‐ray diffraction. The substitution of Cl− by CN− in fac‐[Pt(C^N)2(C6F5)Cl] [C^N=2‐phenylbenzothiazole (3 c), 2‐(4‐bromophenyl)benzothiazole (3 d)] evolved with isomerization to give rise to the isomers (OC‐6–42)‐[Pt(C^N)2(C6F5)(CN)] (4 c, 4 d) having a mer disposition of the cyclometalated and C6F5 groups (X‐ray, 4 c). All the complexes are luminescent and their electronic spectra have been compared and interpreted with the aid of time‐dependent DFT calculations.