Harnessing surface plasmon of metal nanostructures to promote catalytic organic synthesis holds great promise in solar-to-chemical energy conversion. High conversion efficiency relies not only on broadening the absorption spectrum but on coupling the harvested energy into chemical reactions. Such coupling undergoes hot-electron transfer and photothermal conversion during the decay of surface plasmon; however, the two plasmonic effects are unfortunately entangled, making their individual roles still under debate. Here, we report that in a model system of bimetallic Au-Pd core-shell nanostructures the two effects can be disentangled through tailoring the shell thickness at atomic-level precision. As demonstrated by our ultrafast absorption spectroscopy characterizations, the achieved tunability of the two effects in a model reaction of Pd-catalyzed organic hydrogenation offers a knob for enhancing energy coupling. In addition, the two intrinsic plasmonic modes at 400-700 and 700-1000 nm in the bar-shaped nanostructures allow for utilizing photons to a large extent in full solar spectrum. This work establishes a paradigmatic guidance toward designing plasmonic-catalytic nanomaterials for enhanced solar-to-chemical energy conversion.