Highly active metal nanoparticles are desired to serve in high-temperature electrocatalysis, for example, in solid oxide electrochemical cells. Unfortunately, the low thermal stability of nanosized particles and the sophisticated interface requirement for electrode structures to support concurrent ionic and electronic transport make it hard to identify the exact catalytic role of nanoparticles embedded within complex electrode architectures. Here we present an accurate analysis of the reactivity of oxide electrodes boosted by metal nanoparticles, where all particles participate in the reaction. Monodisperse particles (Pt, Pd, Au and Co), 10 nm in size and stable at high temperature (more than 600 °C), are uniformly distributed onto mixed-conducting oxide electrodes as a model electrochemical cell via self-assembled nanopatterning. We identify how the metal catalysts activate hydrogen electrooxidation on the ceria-based electrode surface and quantify how rapidly the reaction rate increases with proper choice of metal. These results suggest an ideal electrode design for high-temperature electrochemical applications.