<p>The biggest challenge facing the advancement of photocatalytic technology so far is how to achieve the simultaneous and efficient utilization of photogenerated electrons and holes for dual value-added chemicals. Here we show that Pd/TiO₂ with electronic metal-support interaction realizes photocatalytic H₂O₂ evolution coupled with furfural selective oxidation to furoic acid. We demonstrate that the electronic structure of Pd is modulated to form Pd^δ+ active sites and upshifted <i>d</i>-band center via electronic metal-support interaction, enhancing O₂ adsorption and H₂O₂ evolution performance, and the photogenerated holes from TiO₂ oxidize furfural undergoing the Aldehyde-Water Shift to furoic acid by sequential breaking of O-H and C-H bonds. The optimal Pd/TiO₂ achieves H₂O₂ and furoic acid evolution rates of 3672.31 and 4529.08 μM h⁻¹ with furfural conversion of 92.66% and furoic acid selectivity of 97.82%. Our work provides a promising approach for enhancing synergistic photosynthesis of dual value-added chemicals, thus advancing carbon neutrality goals.</p>