A thiophene-functionalized methacrylate monomer (3-methylthienyl methacrylate) was synthesized via the esterification of 3-thiophene methanol with methacryloyl chloride. The methacrylate monomer was polymerized by free-radical polymerization in the presence of azobisisobutyronitrile as the initiator. Graft copolymers of poly(3-methylthienyl methacrylate) (PMTM2) and polypyrrole and of PMTM2 and polythiophene were synthesized by constant-potential electrolyses. p-Toluene sulfonic acid, sodium dodecyl sulfate, and tetrabutylammonium tetrafluoroborate were used as the supporting electrolytes. PMTM2-coated platinum electrodes were used as anodes in the polymerization of pyrrole and thiophene. Moreover, the oxidative polymerization of poly(3-methylthienyl methacrylate) (PMTM1) was studied with FeCl3 as the oxidant. The self-polymerization of PMTM1 was also investigated by galvanostatic electrolysis both in dichloromethane and in propylene carbonate. The structures of PMTM1 and PMTM2 were investigated by several spectroscopic and thermal methods. The grafting process was elucidated with conductivity measurements, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and scanning electron microscopy studies.