The X‐ray study on a single crystal of the butterfly‐like complex [{Pt(C^C*)(μ‐pz)}2] (1), containing a cyclometalated N‐heterocyclic carbene ligand as wings (HC^C*=1‐(4‐(ethoxycarbonyl)phenyl)‐3‐methyl‐1H‐imidazol‐2‐ylidene), showed three molecules in the asymmetric unit with intermetallic separations (Å) of 3.2294(4) (1A), 3.2834(4) (1B), and 3.1208(6) (1C). From the reaction of 1 with excess of CHI3 in the air and the sunlight, complex [{Pt(C^C*)(μ‐pz)I)}2] (2) (dPt−Pt=2.6079(2) Å) was obtained as the major product, while [IPt(C^C*)(μ‐pz)2Pt(C^C*)CHI2] (3) (dPt−Pt=2.6324(3) Å) was obtained as the major product under argon atmosphere in the dark. Experimental and theoretical investigations showed that an easily accessible radical‐like mechanism operates under thermal conditions, with dioxygen acting as an efficient radical (R.) scavenger. The oxidation of a Pt2(II,II) “butterfly” by CHI3 to give metal−metal bonded Pt2(III,III) compounds is described now for the first time.