Composite electrodes for supercapacitors are prepared via template synthesis by the electrochemical polymerization of 3-methyl thiophene in the heterogeneous void spaces of polyvinylidene fluoride (PVDF) porous films. The large pore size distribution in the template matrix results in some of the poly(3-methyl thiophene) growing in a more ordered fashion than in films synthesized without spatial restriction, and this can lead to improved conductivity and kinetics. In this work, the capacitance properties of a poly(3-methyl thiophene)/PVDF composite were investigated using cyclic voltammetry, ac impedance spectroscopy and charge–discharge tests. The P(3-MeT)/PVDF|PC/EC/1molL−1 LiClO4|P(3-MeT)/PVDF type III capacitor had a specific capacitance of 616Fg−1 and a Coulombic efficiency of 93%. The power density decreased during ∼300 cycles and then became practically constant at 7.3kWkg−1. These results indicate that template synthesis is an useful alternative to enhance the properties of conducting polymers.