Disposing of end-of-life photovoltaic (PV) modules has posed a significant environmental challenge due to the absence of proficient and sustainable recycling technologies. Separating PV modules, which are ethylene–vinyl acetate (EVA)-bonded layers, including glass, solar cells (i.e., silicon wafers), and backsheets, establishes a foundation for effectively reclaiming valuable resources from PV modules. Removing EVA encapsulation is critical for disassembling PV modules; nonetheless, effective and feasible technology is currently limited. Conventional EVA dissolving agents (e.g., benzene and trichloroethylene) are highly toxic and effective only for non-cross-linked segments of EVA. Thus, developing efficient and environmentally benign reagents for PV waste recycling is urgently needed. Herein, a novel recycling route employing deep eutectic solvents (DESs) with switchable hydrophilicity has achieved successful separation of the component layers within PV modules. Complete separation of the glass and backsheet bonded by the EVA film was achieved under atmospheric pressure and moderate temperature conditions (80 °C for 2 h) by hydrophobic DESs composed of menthol and decanoic acid ([Men][DecA] (1:1)). [Men][DecA] effectively induced EVA swelling, concurrently accelerating EVA dissolution by substituting the acetate groups in the side chains of EVA with the hydroxyl groups of the DES. The superior PV module disintegration can be attributed to the exceptional EVA dissolution ability of the [Men][DecA] framework, and the achieved high solid–liquid ratio (40 g/L) for EVA in [Men][DecA] is beneficial for industrial processes. Furthermore, the reusability of [Men][DecA], which is endorsed by its switchable hydrophilicity, introduces a sustainable platform for PV module disintegration, thereby facilitating the large-scale recycling of PV waste.