AbstractOrganic/silicon hybrid solar cells have attracted extensive attention owing to their low cost and simple manufacturing process. However, theoretical simulations indicate that the efficiency of organic/silicon hybrid solar cells should exceed 20%. This study demonstrates phosphorus and selenium co‐doped WO3 nanoparticles used for heterojunction solar cell (HSC) modification and theoretically elaborates the effects of these doping elements. The doped WO3 nanoparticles are added into poly(3,4‐ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS) films to optimize the physical properties and qualities of the organic layer. The admixture of P/Se‐WOx greatly improves the open‐circuit voltage and fill factor of Si/PEDOT:PSS solar cell devices. In the hole transport layer (HTL)‐based device, the P/Se‐WOx hybrid PEDOT:PSS HTL yields a power conversion efficiency up to 13.64%, which is substantially higher than those of previously reported undoped and doped devices. The generated W5+ in optimized WO3 further indicates that the VI B group elements, such as W or Mo with 5+ state ions, positively influence the HSC performance and would greatly benefit the photovoltaic industry.