We report highly efficient small molecule solar cells (SMSCs) by using dichloromethane solvent vapor annealing method. The resulted devices delivered a power conversion efficiency (PCE) of 8.3%, which is among the highest in SMSCs. Comparing to the control devices, the short circuit current (Jsc), fill factor, and PCE of solvent vapor annealed devices are significantly improved. Summarizing the results of optical absorption, film morphology, and charge carrier transporting properties, we see that the enhanced structure order and reduced size of phase separation are major reasons for the improved device performances, establishing a solid structure-property relationship. The solvent vapor annealing method can thus be a useful method in device fabrication to enhance performances of SMSCs.