Abstract The self‐organization of the polymer in solar cells based on regioregular poly(3‐hexylthiophene) (RR‐P3HT):[6,6]‐phenyl C 61 ‐butyric acid methyl ester (PCBM) is studied systematically as a function of the spin‐coating time t s (varied from 20–80 s), which controls the solvent annealing time t a , the time taken by the solvent to dry after the spin‐coating process. These blend films are characterized by photoluminescence spectroscopy, UV‐vis absorption spectroscopy, atomic force microscopy, and grazing incidence X‐ray diffraction (GIXRD) measurements. The results indicate that the π‐conjugated structure of RR‐P3HT in the films is optimally developed when t a is greater than 1 min ( t s ∼ 50 s). For t s < 50 s, both the short‐circuit current ( J SC ) and the power conversion efficiency (PCE) of the corresponding polymer solar cells show a plateau region, whereas for 50 < t s < 55 s, the J SC and PCE values are significantly decreased, suggesting that there is a major change in the ordering of the polymer in this time window. The PCE decreases from 3.6 % for a film with a highly ordered π‐conjugated structure of RR‐P3HT to 1.2 % for a less‐ordered film. GIXRD results confirm the change in the ordering of the polymer. In particular, the incident photon‐to‐electron conversion efficiency spectrum of the less‐ordered solar cell shows a clear loss in both the overall magnitude and the long‐wavelength response. The solvent annealing effect is also studied for devices with different concentrations of PCBM (PCBM concentrations ranging from 25 to 67 wt %). Under “solvent annealing” conditions, the polymer is seen to be ordered even at 67 wt % PCBM loading. The open‐circuit voltage ( V OC ) is also affected by the ordering of the polymer and the PCBM loading in the active layer.