Two fluorene-based conjugated polymer electrolyte (CPE) poly[(9,9-bis(6'-(N,N,N-trimethylammonium)hexyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFNBr) and poly[9,9-bis(4'-sulfonatobutyl) fluorene-alt-2,7-(9,9-dioctylfluorene)] sodium salt (PFSO3Na), bearing amine groups and anionic sulfonate groups on side chains respectively, are synthesized and applied as cathode interlayer in polymer solar cells. Both of the hydrophilic CPEs can well modify the interfacial properties and allow ohomic contact between the activelayer and cathode. The opposite charges exert great influence on the effective work function of cathode and interfacial interaction through the orientation of the interfacial dipole at the active layer/metal electrode interface, subsequently influence the resulting device performance. Compared with the cationic PFNBr, PFSO3Na with anionic sulfonate groups can dramatically reduce the work function of Al by accumulation of the polar groups at the PFSO3Na/Al interface to induce more favorable the interfacial dipole. The better energy alignment for electron extraction and transportation at active layer/Al interface is confirmed by a significant enhancement of V-OC. The better wettability and morphology of PFSO3Na on the active layer and the more effective motion of sodium counterion further modify the barrier to facilitate electron extraction and transportation. Moreover, 14% and 22% performance enhancement can also be achieved respectively, when PFNBr and PFSO3Na are used as interlayers for low bandgap poly[N-9 ''-heptadecanyl-2,7-carbazolealt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT)-based solar cells. (C) 2013 Elsevier B. V. All rights reserved.