<p>Electrochemical recycling of waste polyethylene terephthalate (PET) plastics represents a green and sustainable route to produce valuable fuels and address serious environmental issues. Despite some encouraged achievements, their progress is still slower because of the lack of highly active and selective electrocatalysts. Here, we reported an efficient PET recycling route with trimetallic PdCuRu mesoporous nanospheres (MSs) as a high-performance electrocatalyst that achieved selective electro-synthesis of valuable formate from PET hydrolysate (PETH) electrooxidation. Penetrated metal mesopores and trimetallic compositions of PdCuRu MSs synergistically optimized electronic structures of Pd sites and changed chemisorption properties of intermediates, which disclosed a high formate Faradic efficiency of 97% and impressive yield rate of 0.49 mmol h⁻¹ cm⁻² in an alkaline solution. Meanwhile, this electrocatalyst held good electrocatalytic stability, retaining high formate Faradic efficiency and yield rate even being performed for 10 cycles, which highlighted its potential applications for practical PET recycling. Our study provides a powerful strategy for designing high performance electrocatalysts toward selective electro synthesis of valuable fuels from various waste plastics.</p>