Organic solar cells based on bulk heterojunction (BHJ) structures have attracted considerable attention because of their low fabrication cost, mechanical flexibility, and compatibility with solution-processing techniques. In BHJ organic photovoltaic devices, nanoscale morphology and crystallinity of the photoactive layer critically influence photovoltaic performance. In this study, the effects of solvent selection and thermal annealing on crystallization evolution and photovoltaic characteristics of P3HT:PCBM organic solar cells were systematically investigated. Three different solvents, including toluene, chlorobenzene (CB), and dichlorobenzene (DCB), were employed for active-layer fabrication, followed by post-thermal annealing treatment. UV–visible absorption spectroscopy revealed solvent-dependent differences in molecular ordering and intermolecular π–π interactions within the active layer. X-ray diffraction analysis confirmed that thermal annealing significantly enhanced crystallinity and lamellar ordering of P3HT domains, particularly for CB-processed films. Electrical characterization demonstrated that solvent evaporation behavior strongly affects photovoltaic performance. Among the investigated devices, the thermally annealed CB-processed device exhibited the highest power conversion efficiency of 1.83% with an enhanced short-circuit current density of 7.057 mA cm⁻². The improved device performance is attributed to optimized crystallization behavior and balanced nanoscale phase separation induced by the moderate evaporation characteristics of CB. In contrast, although DCB-assisted films exhibited relatively strong optical absorption and enhanced crystallinity, excessively slow solvent evaporation likely induced excessive aggregation and coarse phase separation, limiting efficient photovoltaic characteristics. These results demonstrate that solvent engineering combined with thermal annealing is an effective strategy for controlling morphology evolution and crystallization behavior in P3HT:PCBM bulk heterojunction solar cells.