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.