AbstractControlled incorporation of single atoms in a suitable host matrix can result in a radical transformation in catalytic properties. However, finding a straightforward synthetic strategy that offers a compelling combination of solution processing, atomic doping and a matching host is still a grand challenge. Here, a spontaneous heteroatom formation of atomic Zn sites in well‐defined wurtzite CoO nanorods, delivering high photoreduction rates, reaching 86.7 µmol g⁻¹ h⁻¹ for CO and 31.4 µmol g⁻¹ h⁻¹ for CH₄ production is reported. Based on the validation of atomic Zn sites structures, catalytic process tracking via in situ/ex situ spectroscopic probes, and related structural simulations, a good description of the catalytic reaction kinetics for Zn/CoO as a function of applied potential is established, revealing how the single doping sites influence the CO₂ photoreduction.