<p>Overheating remains a major barrier to chip miniaturization, leading to device malfunction. Addressing the urgent need for thermal management promotes the development of solid-state electrocaloric cooling. However, enhancing passive heat dissipation through two-dimensional materials in electrocaloric polymers typically compromises the electrocaloric effect. In this work, we utilize two-dimensional polyamide with porous structure and hydrogen bonding to achieve multiple polar conformations with short-range order in the electrocaloric composite polymers. The structure minimizes intermolecular interactions while reducing energy barriers for field-driven polar-nonpolar conformational transitions. The electrocaloric polymer exhibits doubled cooling efficiency at electric fields as low as 40 MV m⁻¹. Additionally, the electrode design achieves a vertical deformation of 2 millimeters, demonstrating the feasibility of self-driven electric refrigeration devices. This porous organic two-dimensional material resolves cooling efficiency limitations from spatial confinement, advancing the integration of two-dimensional materials in flexible electronics.</p>