Recycling gold from electronic waste represents a sustainable and environmentally friendly strategy for both resource recovery and waste reduction. In this study, we designed an innovative and highly stable porous aromatic framework (PAF)/polymer composite, PAF-147/polydopamine (PDA), as an efficient adsorbent for selective gold recovery for the first time. The maximum gold adsorption capacity of PAF-147/PDA reached 1700 mg·g⁻¹. Furthermore, it could rapidly extract over 95% of gold from solutions in a pH range of 0-10 within just 2 minutes. Importantly, as a real application demonstration, the PAF-147/PDA composite selectively recovered 99% of gold from the leachate of discarded central processing units. When the recovered Au-containing composite was applied to electrocatalytic CO2 reduction, the Faradaic efficiency for CO production exceeded 95% across acidic, neutral, and alkaline electrolytes, outperforming most reported gold-based catalysts due to the cooperation effect of the composite and Au. This work opens a new way for the combination of selective gold recovery from electronic waste with highly efficient CO2 conversion.