We synthesized a series of polychlorinated trityl radical substituted phenylphosphines. Through UV-vis photoluminescence (PL) spectroscopy and cyclic voltammetry, we explored the influence of the chemical modifications (oxidation/reduction, coordination, and methylation) of the phosphorus center(s) on tuning the optical and redox properties of the tris(2,4,6-trichlorophenyl)methyl (TTM) radical framework. Those compounds hold promise for applications in coordination chemistry and luminescent materials, particularly in systems where both radical and phosphine-based functionalities can be leveraged for innovative properties.