Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) is one of the most widely used hole transporting materials in organic solar cells (OSCs).Multiple strategies have been adopted to improve the conductivity of PEDOT∶PSS,however,effective strategy that can optimize the conductivity,work function,and surface energy simultaneously to reach a better energy alignment and interface contact is rare.Here,we demonstrate that oxoammonium salts (TEMPO+X-) with different counterions can act as facile and novel dopants to realize secondary doping of PEDOT∶PSS.The effective charge transfer process achieved between TEMPO+X-and PEDOT∶PSS results in enhanced carrier density and improved conductivity of PEDOT∶PSS.Moreover,different counterions of TEMPO+X-can tune the work function and surface energy of PEDOT∶PSS,enabling improved device performances.The resulting device with PM6∶Y6 as the active layer shows a high power conversion efficiency (PCE) over 16%.Moreover,this doping strategy can also be applied to other conjugated polymers such as poly(3-hexylthiophene).This work provides a promising strategy to tune the properties of conjugated polymers through doping,thus effectively boosting the performance of organic solar cells.