Controlled synthesis of conjugated polymers with functional side chains is of great importance, affording well-defined optoelectronic materials possessing enhanced stability and tunability as compared to their alkyl-substituted counterparts. Herein, a chain-growth Suzuki polycondensation of an ester-functionalized thiophene is described using commercially available nickel precatalysts. Model compound studies were used to identify suitable catalysts, and these experiments provided guidance for the polymerization of the ester-substituted monomer. This is the first report of nickel-catalyzed Suzuki cross-coupling for catalyst-transfer polycondensation, and to further illustrate the versatility of this method, block and alternating copolymers with 3-hexylthiophene were synthesized. The presented protocol should serve as an entry point into the synthesis of other electron-deficient polymers and donor-acceptor copolymers with controlled molecular weights and low dispersity.