Development of simple methods for preparation of polymeric electrode materials with nanofibrous network structure is a perspective way toward cheap supercapacitors with high specific capacitance and energy density. In this work one-pot synthesis of electroactive ternary composite based on polypyrrole, polyacrylamide and chitin nanofibers with beneficial morphology was elaborated. Ternary system demonstrates better electrochemical performance in comparison with both polypyrrole–polyacrylamide and polypyrrole–chitin binary composites. Possible mechanism of synergistic effect of simultaneous influence of polyacrylamide and chitin nanofibers on the formation of composite's structure is discussed. The highest attained specific capacitance of electroactive polypyrrole in ternary composite reached 249 F/g at 0.5 A/g and 150 F/g at 32 A/g. Symmetrical supercapacitor was assembled using the elaborated electrode material. High specific capacitance 89 F/g and good cycling stability with capacitance retention of 90% after 3000 cycles at 2 A/g were measured.