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Using time\u2010resolved, in situ synchrotron radiography combined with synchronized thermal and electrical measurements, we directly visualize the internal evolution of EDLCs under abusive overcharge. We reveal a progressive, thermally driven failure pathway, distinct from the chemically driven thermal runaway seen in lithium\u2010ion batteries, in which initial electrical instability triggers electrolyte decomposition, vapour formation, and gas accumulation, generating heterogeneous internal pressures that drive electrode collapse, casing deformation, and structural destruction. Post\u2010mortem X\u2010ray Computed Tomography (X\u2010ray CT) and cell tear\u2010down confirm permanent electrode delamination and separator failure, while Gas Chromatography\u2010Mass Spectrometry (GC\u2010MS) analysis of vented gases identifies flammable and potentially toxic species, highlighting acute fire and chemical hazards. 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