In this work, we have explored Re(I) complexes featuring triphenylpnictogen (PnPh3, Pn = P, As, or Sb)-based coligands and bidentate (neutral or monoanionic) luminophores derived from 1,10-phenantroline (phen), as well as from 2-(3-(tert-butyl)-1H-1,2,4-triazol-5-yl)pyridine (H(N-tBu)). The effect of the increasingly heavy elements on the structural parameters, photoexcited-state properties, and electrochemical behavior as well as the hybridization defects and polarization of the Pn atoms was related to the charges of the main luminophores (i.e., phen vs N-tBu) and explored in terms of photoluminescence spectroscopy, X-ray diffractometry, and quantum-chemical methods. Therefore, an in-depth analysis of the bonding, crystal packing, excited-state energies, and lifetimes was assessed in liquid solutions, frozen glassy matrices, and crystalline phases along with a semiquantitative photoactivation study. Notably, by changing the main ligand from phen to N-tBu, an increase in radiative and radiationless deactivation rates (kr and knr, respectively) at 77 K together with a faster photoinduced CO release and fragmentation at room temperature was detected. In addition, a progressively red-shifted phosphorescence was observed with the growing atomic number of the pnictogen atom, along with a boost in kr and knr at 77 K. Down the Vth main group and upon coordination of the Pn atom to the Re(I) center, an increasingly prominent jump of s-orbital participation on the binding sxp3.00-orbitals of the Pn atoms is evidenced. Based on these findings, the ability of these complexes to act as tunable photoluminescent labels able to perform as light-driven CO-releasing molecules is envisioned.