More environmentally friendly polymer solar cells were constructed using a conjugated polymer, poly (2,5-thiophene-alt-4,9-bis(2-hexyldecyl)-4,9-dihydrodithieno[3,2-c:3′,2′h][1,5] naphthyridine-5,10-dione, PTNT, as a donor material in combination with PC71BM as an acceptor in a bulk heterojunction device structure. A non-halogenated processing solvent (o-xylene) and solvent additives that are less harmful to the environment such as 1-methoxynaphthalene (MN) and 1-phenylnaphthalene (PN) were used throughout the study as processing solvents. The most widely used halogenated solvent additives (1,8-diiodooctane (DIO) and 1-chloronaphthalene (CN)) were also used for comparison and to understand the effect of the type of solvent additives on the photovoltaic performances. Atomic force microscopy (AFM) was employed to investigate the surface morphology of the films prepared in the presence of the various additives. The best-performing polymer solar cells provided a high open-circuit voltage of 0.9 V, an efficient fill factor of around 70%, and a highest power conversion efficiency (PCE) of over 6% with the use of the eco-friendlier o-xylene/MN solvent systems. Interestingly, the solvent blend which is less harmful and with low environmental impact gave a 20% rise in PCE as compared to an earlier reported device efficiency that was processed from the chlorinated solvent o-dichlorobenzene (o-DCB).