Waste crystalline silicon (c-Si) solar cells are rich in metal resources. The detachment of ethylene-vinyl acetate (EVA) copolymer is a critical step in the recycling of end-of-life (EoL) c-Si photovoltaic (PV) modules, but a clean and high-efficiency adhesive removal method is absent. In this study, we presented a green solvent-based approach using limonene with ultrasound assistance for the efficient delamination of EVA from c-Si PV modules. By adjusting the concentration of limonene solution, the degree of swelling of EVA was effectively controlled, reducing the risk of battery damage caused by uneven swelling. The application of an ultrasonic physical field to the swelling system expedited the diffusion and penetration of the swelling agent between the EVA layers, while simultaneously supplying energy for the fracture of cross-linking bonds. Under the optimized laboratory-scale condition (70 °C, 0.5 h and 0.1 M limonene), complete separation of the glass and backsheet from the EVA bonding layer was achieved. The intact c-Si solar cells thus have the potential to be fully recovered in subsequent processes. FT-IR tests and density functional theory (DFT) simulations confirmed that under ultrasound conditions, limonene molecules selectively attacked crosslinking bridges and side chains of ethyl vinyl acetate in the EVA molecular chain. This induced the breakdown of the EVA crosslinked network structure, resulting in a reduction in adhesive strength and ultimately achieving interlayer separation in 20min. The findings of this study provide theoretical support and technical insights for the clean and efficient recycling of PV modules.