This manuscript consists of two parts which focus on enhancing control over the polymerization of conjugated polymers. In the first part, the controlled chain-growth character of the polymerization of poly(selenophene) using Pd(Ruphos) as a catalyst system is demonstrated. Next, all-conjugated thiophene fluorene selenophene triblock-copolymers are synthesized in all possible orders using this catalyst. Subsequent, the properties of these advanced structures are assessed using GPC chromatography and H-1 NMR, UV-vis, and fluorescence measurements. DFT calculations were performed to explain the unusual independence of the monomer sequence during the polymerization, traditionally observed in other chain-growth protocols for conjugated polymers.