We demonstrate a novel solution-processed method to fabricate a stable anode buffer layer without any annealing process. As we know, buffer layers in polymer solar cells (PSCs) are always prepared by the traditional high-vacuum thermal evaporation or annealing-treated spin-coating methods, but the fabricating processes are complicated and time-consuming. Here, a solution method without any annealing to fabricate phosphomolybdic acid (PMA) as anode buffers is presented, which brings an obvious improvement of power conversion efficiency (PCE) from 1.75% to 6.57% by optimizing the PMA concentrations and interface pretreatment with device structure shown as ITO/TiO2/PCDTBT:PC70BM/PMA/Ag. The improvement is ascribed to the fine energy-level matching and perfect surface modification. This annealing-free method greatly simplifies the device fabrication process and supplies a wide way to achieve a large area fabrication for PSCs.