Active layers of polymer solar cells were prepared by aerosol jet printing of organic inks. Various solvents and additives with high boiling points were screened for the preparation of high-quality polymer films. The effects on device performance of treating the films by thermal and solvent vapor annealing were also investigated. The components of the solvent were important for controlling the drying rate of the liquid films, reducing the number of particle-like protrusions on the film surface, and realizing high molecular ordering in the polymer phases. The optimized solar cell device with poly(3-hexylthiophene) and a C(60) derivative showed a high fill factor of 67% and power conversion efficiency of 2.53% without thermal annealing. The combination of poly[N-9-heptadecanyl-2,7-carbazole-alt-3,6-bis(thiophen-5-yl)-2,5-diethylhexyl-2,5-dihydropyrrolo-[3,4-]pyrrole-1,4-dione] and a C(70) derivative led to power conversion efficiency of 3.92 and 3.14% for device areas of 0.03 and 1 cm(2), respectively.