In the frame of our research aiming to develop efficient triplet-emitting materials, we are exploring the concept of introducing additional heavy atoms into cyclometalated transition metal complexes to enhance intersystem-crossing (ISC) and thus triplet emission through increased spin–orbit coupling (SOC). In an indepth proof-of-principle study we investigated the double cyclometalated Pt(II) complexes [Pt(C^N^C) (PnPh3)] (HC^N^CH = 2,6-diphenyl-pyridine (H2dpp) or dibenzoacridine (H2dba); Pn = pnictogen atoms P, As, Sb, or Bi) through a combined experimental and theoretical approach. The derivatives containing Pn =P, As, and Sb were synthesised and characterised comprehensively using single crystal X-ray diffraction (scXRD), UV-vis absorption and emission spectroscopy, transient absorption (TA) spectroscopy and cyclic voltammetry (CV). Across the series P < As < Sb, a red-shift is observed concerning absorption and emission maxima as well as optical and electrochemical HOMO–LUMO gaps. Increased photoluminescence quantum yields ÖL and radiative rates kr from mixed metal-to-ligand charge transfer (MLCT)/ligand centred (LC) triplet states are observed for the heavier homologues. Transient absorption spectroscopy showed processes in the ps range that were assigned to the population of the T1 state by ISC. The heavy PnPh3 ancillary ligands are found to enhance the emission efficiency due to both higher Pt–Pn bond strength and stronger SOC related to increased MLCT character of the excited states. The experimental findings are mirrored in hybrid (TD-)DFT calculations. This allowed for extrapolation to the rather elusive Bi derivatives, which were synthetically not accessible. This shortcoming is attributed to the transmetalation of phenyl groups from BiPh3 to Pt, as supported by experimental NMR/MS as well as DFT studies.