Two-dimensional numerical simulations using compressible reactive Navier–Stokes equations and detailed thermochemical mechanisms were performed to investigate the impact of ozone doping on detonation wave structures in the stoichiometric hydrogen–air mixture. In the hydrogen–air mixture, ozone acts as an ignition promoter, releasing reactive oxygen radicals during high-temperature decomposition. These radicals accelerate chain-branching reactions, enhancing ignition kinetics and significantly reducing detonation length and timescales. Ozone doping leads to a reduction in detonation cell size and an increase in the number of transverse waves, improving detonation stability. Higher ozone concentrations further reduce detonation cell size, creating a more uniform and stable detonation pattern, thereby enhancing detonation propagation. In mixtures containing ozone and inert diluents like argon, the detonation cells become more regular but slightly larger. Although argon’s thermal inhibiting effect increases induction length, ozone maintains high reactivity, ensuring a stable detonation structure. These results highlight the critical role of ozone in optimizing detonation wave stability and performance, demonstrating its potential for improving pressure-gain combustion technologies such as rotating and pulse detonation engines. Furthermore, the study emphasizes the importance of controlling ozone concentrations in practical engine applications for improved efficiency. Future investigations could explore the effects of other additives or different fuel-oxidizer combinations to further enhance detonation characteristics.