During coupling with carbon dioxide reduction reactions (CO2RR), plastic reforming as an effective alternative anodic reaction to replace oxygen evolution reaction (OER), offers dual benefits of reducing energy consumption and producing valuable chemicals. However, balancing the energy requirements of polyethylene terephthalate (PET) oxidation with CO2RR is challenging, as both half-reactions must operate under compatible conditions for high efficiency. Here, it is developed a bifunctional copper hydroxide catalyst capable of simultaneously converting both PET and CO2 into valuable chemicals, which simplifies the system complexity. The copper hydroxide-derived catalyst achieves a formate FE of 89.5% produced on anode and an ethylene FE of 60.8% on cathode. It is discovered that CuOOH forms when Cu(OH)(2) is immersed in an EG electrolyte, enhancing EG adsorption and promoting its oxidation. After pre-reduction, the Cu(OH)(2)-derived catalyst shows increased exposure of Cu(100) facets and enhanced C-C coupling for CO2 reduction to ethylene. Driven by a silicon solar cell module, the product formation rates of 4.72 mmol/h/cm(2) (formate) and 9.65 mmol/h/cm(2) (ethylene) is achieved by the system at a current density of 302.7 mA/cm(2). This work proposes a sustainable strategy utilizing a bifunctional catalyst for solar electrochemical upcycling of PET plastic, coupled with CO2 reduction, to generate value-added fuels.