Multi-layer plastic films are widely used in various fields especially for packaging, but due to complex composition, it is very difficult to recover single-material polymers or high-purity monomers from them after usage. In this study, we proposed a hydrothermal process for recycling PET/PE (PET: Polyethylene terephthalate; PE: Polyethylene) films. PET can be hydrolyzed to monomers of terephthalic acid (TPA) and ethylene glycol (EG). Using a hydrothermal system equipped with two filters, PE, TPA, and EG were collected separately, indicating the simultaneous material and chemical recycling of PET/PE films was firstly achieved. At 300 °C and 10 MPa for 60 min, PET conversion reached around 100%, and TPA yield of 83.0% was obtained with a high TPA purity of 96.1%. In addition, the effect of the holding time on PET conversion, TPA yield, EG yield, and TPA purity was studied. This research opened up a new and sustainable pathway to recycle multi-layer plastic films in both lab and industry.