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Inverted solution-processed SMPV1:PC₇₁BM small molecule organic photovoltaic solar cells (SM-OPVs) were fabricated. The power conversion efficiency (PCE) of halogen-free SM-OPVs reached around 5.07%. The absorption spectra at different device thicknesses were simulated by software Fluxim SETFOS 5.0, and compared with the experimental results. To further enhance the performance of halogen-free SM-OPVs, the interface between the active layer and the electrode of the optimized device was treated with the solvent vapor annealing (SVA) process, improving the PCE of the inverted halogen-free SM-OPV to 7.21%.