Polymer solar cells (PSCs) with poly(3‐hexylthiophene) (P3HT) as a donor, an indene‐C70 bisadduct (IC70BA) as an acceptor, a layer of indium tin oxide modified by MoO3 as a positive electrode, and Ca/Al as a negative electrode are presented. The photovoltaic performance of the PSCs was optimized by controlling spin‐coating time (solvent annealing time) and thermal annealing, and the effect of the spin‐coating times on absorption spectra, X‐ray diffraction patterns, and transmission electron microscopy images of P3HT/IC70BA blend films were systematically investigated. Optimized PSCs were obtained from P3HT/IC70BA (1:1, w/w), which exhibited a high power conversion efficiency of 6.68%. The excellent performance of the PSCs is attributed to the higher crystallinity of P3HT and better a donor–acceptor interpenetrating network of the active layer prepared under the optimized conditions. In addition, PSCs with a poly(3,4‐ethylenedioxy‐thiophene):poly(styrenesulfonate) (PEDOT:PSS) buffer layer under the same optimized conditions showed a PCE of 6.20%. The results indicate that the MoO3 buffer layer in the PSCs based on P3HT/IC70BA is superior to that of the PEDOT:PSS buffer layer, not only showing a higher device stability but also resulting in a better photovoltaic performance of the PSCs.