Copolymers of 5-vinyl-2,2′-bithiophene with methyl methacrylate or n-butyl acrylate were synthesized. Copolymer compositions were analyzed by nuclear magnetic resonance spectroscopy and reactivity ratios were calculated using the Kelen-Tudos method. 5-Vinyl-2,2′-bithiophene proved to be a very reactive monomer with a reactivity ratio value of greater than 3 in copolymerization reactions with methyl methacrylate and a value of greater than 4 in Copolymerization reactions with n-butyl acrylate.