The influence of the solvent on the morphology and performance of polymer solar cells is investigated in devices based on blends of the polyfluorene copolymer, poly(2,7-(9,9-dioctyl-fluorene)-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)), and [6,6]-phenyl-C61-butyric acid methyl ester. The blends are spin-coated from chloroform or from chloroform mixed with small amounts of xylene, toluene, or chlorobenzene. The devices are characterized under monochromatic light and solar illumination AM1.5 (AM: air mass). An enhancement of the photocurrent density is observed in diodes made from chloroform mixed with chlorobenzene, and reduced photocurrent density is observed in diodes made from chloroform mixed with xylene or toluene, compared to diodes made from neat chloroform. The open-circuit voltages are almost the same in all diodes. The surfaces of the active layers are imaged using atomic force microscopy. Height images indicate that a finer and more uniform distribution of domains corresponds to the diodes with enhanced photocurrent that are made from chloroform mixed with chlorobenzene, while a structure with larger domains is associated with the lower photocurrents in the diodes made from chloroform mixed with xylene or toluene. The influence of the morphology on the excited-state dynamics and charge generation is investigated using time-resolved spectroscopy. Fast formation of bound charge pairs followed by their conversion into free charge carriers is resolved, and excitation-intensity-dependent non-geminate recombination of free charges is observed. A significant enhancement in free-charge-carrier generation is observed on introducing chlorobenzene into chloroform. Imaging photocurrent generation from the solar cells with a light-pulse technique shows an inhomogeneous photocurrent distribution, which is related to the undulations in the thickness of the active layer. Thicker parts of the diodes yield higher photocurrent values.