A series of six diketopyrrolopyrrole (DPP) based conjugated polymers with a varying content of solubilizing perfluoroalkyl chains were synthesized. Based on a systematic investigation of the influence of the solvent on the photovoltaic performance, it is found that 1,6-diiodoperfluorohexane (IC6F12I) is an effective solvent additive to enhance the power conversion efficiency (PCE) of DPP polymers with perfluoroalkyl side chains. The polymers consist of thiazole-flanked DPP units that alternate along the main chain with varying ratios of thiophene (T) and perfluoroalkyl benzodithiophene (FBDT) units. The polymers possess high molecular weights, narrow band gaps and good crystalline properties. The DPP polymers were used as electron acceptors in bulk heterojunction solar cells with another DPP polymer as the electron donor. A solvent mixture of CHCl3:1-chloronaphthalene (1-CN) is found to provide the best PCE of 2.9% in non-fluorine based DPP polymer solar cells, but yields a low PCE of 0.52% for perfluoroalkyl-containing polymer solar cells. Perfluoroalkyl-containing polymer solar cells fabricated from CHCl3 with IC6F12I as the processing additive show a significantly improved PCE of 2.1%. The morphology analysis of the blend films reveals that IC6F12I as an additive improves the micro-phase separation between the polymer donor and acceptor, which results in enhanced charge generation.