For the first time, chemical and electrochemical grafting of polythiophene (PTh) onto poly(methyl methacrylate) (PMMA) via a combination of atom transfer radical polymerization (ATRP), and Grignard reaction is reported. For this purpose, a PMMA was synthesized by ATRP technique, and then reacted with 2-thienylmagnesium bromide to afford a thiophene-functionalized PMMA macromonomer. The synthesized macromonomer was subsequently used in chemical and electrochemical oxidation copolymerization methods with thiophene monomer to produce PMMA-g-PTh copolymer. In addition, the solutions of the chemically synthesized PMMA-g-PTh copolymer, and gelatin was electrospun to produce uniform, and conductive nanofibers. The chemical structures of all samples as representatives were characterized by means of Fourier transform infrared, and H-1 nuclear magnetic resonance spectroscopies. The electroactivity behaviors of the synthesized samples were verified under cyclic voltammetric conditions, and their conductivities were determined using the four-probe technique.