This study elucidates the long-term mobilization mechanisms of potentially toxic elements (PTEs) from coal and gangue in the Ordos Basin, a representative arid/semi-arid region experiencing seasonal freeze-thaw (F-T) cycles. We conducted a 360-day field-based static leaching experiment under natural environmental conditions, integrated with Tescan Integrated Mineral Analyzer(TIMA)-based quantitative mineralogical mapping, sequential extraction, and kinetic modeling. The results demonstrate that PTE release follows a distinct three-stage pattern: an initial rapid leaching phase dominated by water-soluble fractions, a winter stagnation phase, and a critical post-thaw secondary release pulse. Notably, thawing significantly enhanced the release of Cr, Cd, and Ni, suggesting that F-T cycles accelerate physical weathering and activate previously immobilized fractions. TIMA analysis identifies biotite, ankerite, albite, and pyrite as important PTE hosts, directly linking these mineral phases to the observed kinetic divergence: Co, Cr, Pb, Zn, and Cu are primarily governed by diffusion-controlled processes, whereas Ni, Cd, and As follow surface reaction-controlled kinetics. Crucially, gangue from Jurassic strata exhibited a higher cumulative release potential and greater climatic sensitivity than coal, identifying it as a priority source for long-term pollution control. These findings indicate that conventional laboratory leaching tests may severely underestimate PTE emissions in seasonally frozen regions, highlighting the urgent need for site-specific climate-adaptive management strategies in seasonally frozen mining regions such as the Ordos Basin, with priority attention to Jurassic strata gangue which exhibits high climatic sensitivity.