Polyaniline nanofibres of high conductivity were prepared by interfacial polymerization. The polyaniline nanofibres were used as an active cathode material in lithium-polymer cells. Gel polymer electrolyte (GPE) based on the porous poly(vinylidene-co-hexafluoropropylene) P(VdF-co-HFP), membrane was prepared and used as an electrolyte material in assembling Li/GPE/polyaniline cells. The electrochemical properties of the cells were investigated by cyclic voltammetry and charge–discharge cycling tests. The cell delivered a maximum discharge capacity of 69mAhg−1 at 20th cycle and 48mAhg−1 at 100th cycle with 97% coulombic efficiency.