In this study, it is demonstrated that the radiative rate constant of phosphorescent metal complexes can be substantially enhanced using monodentate ancillary ligands containing heavy donor atoms. Thus, the chlorido coligand from a Pt(II) complex bearing a monoanionic tridentate C^N*N luminophore ([PtLCl]) was replaced by triphenylphosphane (PPh3) and its heavier pnictogen congeners (i.e., PnPh3 to yield [PtL(PnPh3)]). Due to the high tridentate-ligand-centered character of the excited states, the P-related radiative rate is rather low while showing a significant boost upon replacement of the P donor by heavier As- and Sb-based units. The syntheses of the three complexes containing PPh3, AsPh3, and SbPh3 were completed by unambiguous characterization of the clean products using exact mass spectrometry, X-ray diffractometry, bidimensional NMR, and 121Sb-Mössbauer spectroscopy (for [PtL(SbPh3)]) as well as steady state and time-resolved photoluminescence spectroscopies. Hence, it was shown that the hybridization defects of the Vth main-group atoms can be overcome by complexation with the Pt center. Notably, the enhancement of the radiative rate constants mediated by heavier coligands was achieved without significantly influencing the character of the excited states. A rationalization of the results was achieved by TD-DFT. Even though the Bi-based homologue was not accessible due to phenylation side reactions, the experimental data allowed a reasonable extrapolation of the structural features whereas the hybridization defects and the excited state properties related to the Bi-species and its phosphorescence rate can be predicted by theory. The three complexes showed an interesting antiprotozoal activity, which was unexpectedly notorious for the P-containing complex. This work could pave the road toward new efficient materials for optoelectronics and novel antiparasitic drugs.