The modulation of the environment around the “PtI2” molecular fragment in the Pt(IV) cyclometalated complexes [PtI2(ppy) (facac)](1a) and [PtI2(ppy) (acac)] (1b) (Hfacac = hexafluoroacetylacetone; Hacac = acetylacetone) causes competition between halogens in the formation of leading intermolecular interactions. Particularly, the presence of the “organic fluorine” CF3 induces significant structural changes proving the key role that fluorine plays in crystal engineering in metallorganic systems.