Polymer based optoelectronic composites and thin film devices exhibit great potential in space applications due to their lightweight, flexible shape, high photon absorption coefficients, and robust radiation tolerance in space environment. Polymer/dye composites appear promising for optoelectronics applications due to potential enhancements in both light harvesting and charge separation. In this study, the optoelectronic properties of a series of molecular dyes paired with a conjugated polymer Poly(3-hexylthiophene-2,5-diyl) (P3HT) were investigated. Specifically, the solution PL quenching coefficients (Ksv) of dye/polymer follows a descending order from dyes of Chloro(protoporphyrinato)iron(III) (Hemin), Protoporphyrin, to meso-Tetra(4-carboxyphenyl)porphine (TCPP). In optoelectronic devices made of the P3HT/dye/PCBM composites, the short circuit current densities Jsc as well as the overall power conversion efficiencies (PCE) also follow a descending order from Hemin, Protoporphyrin, to TCPP, despite Hemin exhibits the intermediate polymer/dye LUMO (lowest unoccupied molecular orbital) offset and lowest absorption coefficient as compared to the other two dyes, i.e., the cell optoelectronic efficiency did not follow the LUMO offsets which are the key driving forces for the photo induced charge separations. This study reveals that too large LUMO offset or electron transfer driving force may result in smaller PL quenching and optoelectronic conversion efficiency, this could be another experimental evidence for the Marcus electron transfer model, particularly for the Marcus ‘inverted region’. It appears an optimum electron transfer driving force or strong PL quenching appears more critical than absorption coefficient for optoelectronic conversion devices.