Chemical reactions involving nanoparticles often follow complex processes. In this respect, real-time probing of single nanoparticles under reactive conditions is crucial for uncovering the mechanisms driving the reaction pathway. Here, we have captured in situ the oxidation of single Cu nanoparticles to unravel a sequential competitive activation of different mechanisms at temperatures 50–200 °C. Using environmental scanning transmission electron microscopy, we monitor the evolution of oxide formation with sub-nanometre spatial resolution, and show how the prevalence of oxide island nucleation, Cabrera–Mott, Valensi–Carter and Kirkendall mechanisms under different conditions determines the morphology of the particles. Moreover, using in situ electron energy-loss spectroscopy, we probe the localised surface plasmons of individual particles during oxidation, and with the aid of finite-difference time-domain electrodynamic simulations investigate the signature of each mechanism in their plasmonic response. Our results shed light on the rich and intricate processes involved in the oxidation of nanoparticles, and provide in-depth insight into how these processes govern their morphology and optical response, beneficial for applications in catalysis, sensing, nanomedicine and plasmonics.