Two conjugated polymer@activated carbon composites were synthesized by the in situ polymerization of two donor–acceptor type polymers including poly[(thiophene-2,5-yl)-((pyrene-4,5,9,10-tetraone)-2,7-yl)] (PTPT) and poly[((2,3-dihydrothieno[3,4-b][1,4]dioxine)-5,7-yl)-((pyrene-4,5,9,10-tetraone)-2,7-yl)] (POTPT) on activated carbon (AC) by one-step cross-coupling reaction catalyzed by an organometallic catalyst. Cyclic voltammetry showed that both polymers exhibited ambipolar properties, low bandgaps, and low electrode potentials, which could be useful for their application as anodes in lithium-ion battery cells (LIBs). For PTPT@AC and POTPT@AC anodes, they showed a high capacity of 253.9 and 370.5 mA h g−1 at 100 mA g−1. Besides, the capacities of pure polymers were calculated to be 693.5 and 1276.5 mA h g−1 for PTPT and POTPT, respectively, at 100 mA g−1. Compared with PTPT, the introduction of the 3,4-ethylenedioxy unit into the side chain of the thiophene unit leads to substantially improved performance of POTPT due to the lowered LUMO energy levels of POTPT and the electron-rich feature of the EDOT unit. It is suggested that the structure-tuning strategy might be an effective method to prepare the new polymer-based anode for next generation LIBs with high performance and high safety.