Upcycling plastic waste into high-value functional materials provides a compelling strategy to mitigate environmental pollution while enabling sustainable energy technologies, yet it remains a considerable challenge. Although polyethylene terephthalate (PET)-derived metal-organic frameworks (MOFs) have shown encouraging electrocatalytic performance, most are obtained as powders, and their direct growth on conductive substrates is still difficult. Herein, we report a facile synthesis of PET-derived bimetallic NiM-based MOF (M . Zn, Co, Cu) nanowire arrays as highly efficient oxygen-evolving electrocatalysts. Theoretical calculations reveal that bimetallic MOFs exhibit an upshifted d-band center relative to monometallic counterparts, indicating enhanced interactions between active sites and reaction intermediates, which are critical for improved catalytic activity. Among them, NiCu-MOF-15 delivers bifunctional performance toward both the oxygen evolution reaction (OER) and urea oxidation reaction (UOR), achieving overpotentials of 375 and 201 mV to deliver 0.5 A cm−2, respectively. Moreover, NiCu-MOF-15 enables efficient overall water electrolysis across a broad temperature range, requiring only 1.64 V to reach 0.5 A cm−2 at 80°C. Operando Raman spectroscopic analyses identify an in situ-formed amorphous NiOOH layer as the active phase during OER and UOR. This work establishes an effective route for transforming PET waste into high-performance MOF electrocatalysts and provides new insights into coupling plastic waste valorization with sustainable energy conversion.