Ozone olefin reactions may be a significant source of OH in the urban atmosphere, but current evidence for OH production is indirect and contested. We report the first direct observation of OH radicals from the reaction of ozone with a series of olefins (ethene, isoprene, trans‐2‐butene and 2,3 dimethyl‐2‐butene) in 4–6 torr of nitrogen. Using LIF to directly observe the steady‐state of OH produced by the initial ozone‐olefin reaction and subsequently destroyed by the OH‐olefin reaction, we are able to establish OH yields broadly consistent with indirect values. The identification of the OH is unequivocal, and there is no indication that it is produced by a secondary process. To support these observations, we present a complete ab‐initio potential energy surface for the O₃‐ethene reaction, extending from the reactants to available products.