The photovoltaic (PV)-driven electrolysis of polyethylene terephthalate (PET) plastic waste represents a sustainable pathway for resource recovery. Current research predominantly focuses on simulated electrolysis systems or integrated energy storage configurations, while practical implementation under real solar irradiation conditions remains insufficiently investigated. Herein, we report a direct PV-driven electrocatalytic strategy, capable of continuously and simultaneously upcycling PET using a NiOOH electrocatalyst. Remarkably, the catalyst exhibits stable operation for over 500 hours at 300 mA cm⁻² in the laboratory, and it retains a Faradaic efficiency above 86% within 36 hours under real solar light PV-driven conditions. Through catalyst characterization, we reveal that current fluctuations inherent to solar intermittency induce structural degradation of active catalytic species, highlighting the critical need for enhanced stability optimization. This study provides a pioneering proof-of-concept direct PV-driven electrocatalytic strategy and presents a chemical engineering guideline for scaling PV-powered plastic upcycling technologies.