The bulk hetero-junction (BHJ) photovoltaic architecture is applicable to a wide variety of materials and recently conjugated polymers and inorganic semiconductor nanoparticle systems have been investigated. These materials are advantageous for organic photovoltaic (OPV) applications because they combine the strong light harvesting capabilities of the inorganic component with the ability to solution process well-ordered structures for efficient charge separation and migration of the organic component. Colloidal semi-conducting nanocrystals or nanoparticles are often used as the inorganic component in these types of devices, but are often plagued by aggregation of the inorganic particles rather than the preferred dispersion throughout the polymer matrix. Coatings added to the nanoparticles for solubility and stability make it very difficult to understand the interaction between the donor and acceptor from a chemical perspective. Therefore two cobalt selenide clusters with 2-bromo-5-diethylphosphinothiophene (1) and 2-bromo-5-diphenylphosphinothiophene (2) ligands are described. The prepared phosphine ligands are then sequentially reacted with elemental selenium followed by dicobalt octacarbonyl to yield Co6Se8(P(Et)2(C4H2SBr))6 (3) or Co6Se8(P(Ph)2(C4H2SBr))6 (4), respectively. The two new cobalt selenide clusters were characterized by UV-visible spectroscopy, Fourier-transform infared spectroscopy, cyclic voltammetry, and elemental analysis. Emission spectra were recorded for the addition of, Co6Se8(PEt3)6 (5), 3, and 4 to a 0.004 wt% solution of poly-3-hexyl thiophene (P3HT) in toluene to investigate the charge transport of the system. The quenching of the polymers’ emission follows first-order like decay for each cluster. Clusters 3 and 4 are approximately twice as efficient at quenching the emission than cluster 5 with 4 being slightly more efficient than 3. Simple mixtures of 3, 4 or 5 and P3HT were spun cast from toluene into thin films and atomic force microscopy displayed relatively uniform dispersion of 3 and network-like formation of 4 in contrast to the phase separation of 5 in the polymer films. These results indicate that 4 has the ability to not only act as an acceptor but also to form ordered structures, increasing the ability for charge transport in hybrid BHJ devices.