Conventional direct methanol fuel cells (DMFCs) are fundamentally limited by their dependence on noble-metal catalysts and the inevitable release of CO2. Overcoming these barriers requires the design of non-precious alternatives capable of selectively steering methanol oxidation toward formate, avoiding greenhouse gas emissions, but it remains challenging to control. In this work, we present a CO2-free DMFC architecture that utilizes ultra-dispersed CuFe clusters anchored on plastic-recycled hierarchically porous carbon (CuFe/RHPC). This system achieves exceptional electrocatalytic metrics, including a maximum power density of 127.8 mW/cm2 and a current density of 613.83 mA/cm2 at a cell voltage of 0.23 V. Notably, the device demonstrates robust long-term stability over 200 h with 96.9% current-density retention and 99.63% Faraday efficiency for formate synthesis. Mechanistic insights from density functional theory (DFT) reveal that the electronic d-orbital coupling between Cu and Fe facilitates selective partial oxidation by inhibiting the deep oxidation path to CO2. This strategy offers a dual-benefit approach for sustainable energy conversion and waste upcycling through high-performance, non-noble bimetallic electrochemistry.