Formulating a quantitative relationship between the extent of electron transfer at metal-oxide interfaces and catalytic performance aids the rational design of oxide-supported metal catalysts. An effective strategy for monitoring electron transfer at nanoscale interfacial sites is to detect in real time the hot electrons excited when catalytic reactions occur at metal-oxide perimeter sites. Here, based on our in situ techniques for extracting electron transfer as a current signal using a catalytic nanodiode sensor, we observe hot electron excitation at the CeO2/Pt interface during H-2 oxidation. By quantitatively analyzing the hot electrons released during the reaction, we identified the optimal concentration of CeO2/Pt interfaces that maximize the catalytic performance of CeO2/Pt. Through a combinatorial study of experiment and theory, we confirm the decisive role of CeO2/Pt interfacial sites in improving the reactivity and electronic excitation.