Lithium-ion pouch cells exhibit significant irreversible expansion during long-term cycling, which determines overall performance and induces degradation failure without an appropriate mechanical fixture. However, the synergistic mechanism of mechanical pre-torque and battery state on battery electrochemical performance is unclear. To address this issue, this study reveals the electrochemical characteristic evolution of commercial lithium-ion pouch cells during cycling degradation, under varying mechanical pre-torques (0 N·m, 0.5 N·m, 1 N·m, and 1.5 N·m) and at different states of charge (SOCs, 0%, 25%, 50%, 75%, and 100%). Results indicate that moderate pressure (0.5 N·m) optimizes the electrode–electrolyte contact, reducing solid–electrolyte interphase resistance (R_SEI), ohmic resistance (R_O), charge transfer resistance (R_ct), and Warburg coefficient (W) by over 55%, 60%, 30% and 20%, respectively, compared with the free state. High pressure (1.5 N·m) induces impedance rebound due to pore compression, with the increment ranging from 20% to 40%. Furthermore, synergistic impact analysis proves that pressure alters impedance sensitivity to SOC, with changing rates amplifying from <5% per SOC unit under low pressure to 10–15% under high pressure, particularly exacerbating interface passivation at low SOC and side reactions at high SOC. Moreover, a Gaussian process regression (GPR) based adaptive SOC estimation model is developed, incorporating impedance features and pressure paths, achieving a root mean square error of 2.1% and enhancing accuracy by 10–15% over conventional methods in high-pressure scenarios. This study provides guidance for the next-generation pouch cell module design and management.