Ambipolar organic electrochemical transistors (OECTs) can simplify manufacturing processes and reduce device footprints, yet their performance still lags behind their p-type and n-type counterparts due to limited molecular design strategies. Here, incorporating strong proquinoidal building blocks effectively addresses this challenge is demonstrated. Using a computational acceptor screening approach, three TBDOPV-based polymers are designed and synthesized: P(bgTBDOPV-T), P(bgTBDOPV-EDOT), and P(bgTBDOPV-MeOT2), all exhibiting ambipolar behavior across various donor moieties. Remarkably, P(bgTBDOPV-EDOT) achieves record-high figure-of-merit (µC*) values, reaching 268 F cm