This research delved into the oxidation chemistry of 1-hexene with and without the addition of O₃ within a 350–800 K temperature range using a near-atmospheric pressure jet-stirred reactor. Via gas chromatography and mass spectrometry, the products were identified, revealing O₃ ability to enhance fuel oxidation and enabling significant conversion in typically inhibitive conditions (below 500 K and above 700 K). Due to the addition of O₃, efficient fuel conversion is observed at the lowest temperatures, while a significant fuel reactivity persists in the high temperature zone, where the negative temperature coefficient behavior is almost fully suppressed. The addition of O₃ induces an increased production of aldehydes (formaldehyde, acetaldehyde, propanal, butanal, and pentanal) and acids (pentanoic acid) at the lowest temperatures and amplifies the formation of several products (CO₂, CO, butene, butyl-oxirane, 2-butanone, ethylene, methanol, ethanol, furan, acrolein, acetone, propene, butadiene, methyloxirane, ethyloxirane, pentane, and methylvinylketone) at higher temperatures. A significant concentration of ketohydroperoxides is also formed below 500 K. Our experimental findings, compared to the simulations of an updated kinetic model, suggest that ozonolysis at low temperatures and the interaction of O atoms from the thermal decomposition of O₃ with oxidation products at high temperature are responsible for the fuel conversion enhancement by enriching the radical pool. The implications of this study spanning both combustion and atmospheric chemistry domains show that the incorporation of O₃ promises enhanced combustion fuel efficiency and strengthens its potential in optimizing fuel blends, pioneering combustion strategies, and controlling pollution