Single-atom catalysts maximize the utilization of supported precious metals by exposing every single metal atom to reactants. To avoid sintering and deactivation at realistic reaction conditions, single metal atoms are stabilized by specific adsorption sites on catalyst substrates. Here we show by combining photoelectron spectroscopy, scanning tunnelling microscopy and density functional theory calculations that Pt single atoms on ceria are stabilized by the most ubiquitous defects on solid surfaces—monoatomic step edges. Pt segregation at steps leads to stable dispersions of single Pt²⁺ ions in planar PtO₄ moieties incorporating excess O atoms and contributing to oxygen storage capacity of ceria. We experimentally control the step density on our samples, to maximize the coverage of monodispersed Pt²⁺ and demonstrate that step engineering and step decoration represent effective strategies for understanding and design of new single-atom catalysts.