An efficient method for the preparation of a highly conducting hybrid material from graphene oxide nanosheets (GNS) and a novel conjugated polymer, poly(3,4-propylenedioxythiophene), is demonstrated. A functionalized monomer based on 3,4-propylenedioxythiophene, namely ProDOT–OH, was covalently functionalized with GNS, followed by oxidative polymerization to prepare GNS-f-PProDOT composites. The covalent functionalization process of GNS with the monomer ProDOT–OH was activated through the simple esterification reaction between the acyl chloride derivative on the nanosheets and the pendant hydroxyl group present in the monomer. Furthermore, the monomer functionalized GNS were co-polymerized with thiophene resulting in hybrid graphene nanostructures coated with highly conducting co-polymers with a room temperature electrical conductivity as high as 22.5 S cm−1. The resulting hybrid materials were characterized using a range of analytical techniques. The specific capacitance value of the composite and the co-polymer hybrids at a scan rate of 10 mV s−1 has been determined to be 158 and 201 F g−1 respectively and hence particularly promising for supercapacitors.