Metal-organic frameworks (MOFs) show great promise for sodium-ion batteries owing to diverse structures, versatile functionalities, controllable chemical compositions/surface chemistry, adjustable host–guest interactions, and custom-designed pore structure, however, struggling with inferior rate capability because of the polaronic effect induced slow electron transfer. Herein, a polaron breakdown strategy was proposed to enhance the electron transport in MOF (Ni2+ and 2,3,6,7,10,11-hexaaminotriphenylene hexahydrochloride based MOF, NOF). Specifically, the increment entropy strategy was adopted by inserting another metal ion (Cu2+, Co2+, Mn2+) into the crystal lattice of NOF (IE-NOF) to break down the symmetry of 2-dimensional layer and elicited polaron breakdown to rescue the electrons from the self-trapped condition, acquiring fast electron transfer. The electrical conductivity of the as-synthesized IE-NOF-Mn/Co/Cu/Ni (1:1:1:1) is 30 times higher than the pristine NOF. DFT calculation exhibits that IE-NOF-Mn/Co/Cu/Ni (1:1:1:1) breaks down small-polaron to generate highly delocalized electrons and reduce the mutual interaction of Na-N to facilitate the Na+ diffusion, contributing lower energy barrier compared to NOF (0.1 vs 0.5 eV). The anode of IE-NOF-Mn/Co/Cu/Ni (1:1:1:1) shows a high capacity of 551 mAh g−1 at 100 mA g−1, and a high-rate property of 303.1 mAh g−1 at 5 A g−1. The strategy of increment entropy to promote polaron breakdown to enhance charge transfer is conducive to fast-charging battery development.