The gas-phase reaction of OH(X 2 Π ) radicals with di- n-butoxymethane (DBM) has been studied in the temperature range 298–710 K at total pressures between 50 and 100 Torr argon. OH radicals have been generated by excimer laser photolysis of H 2O 2 at 248 nm and have been detected by laser-induced fluorescence. Within the investigated ranges, the reaction has been found to be independent of temperature and total pressure. The bimolecular rate coefficient is k OH+DBM=(3.21±0.79)×10 −11 cm 3 s −1. The rate coefficient is compared with the results from an estimation using structure–activity relationships. Over the whole temperature range, the calculated results are somewhat higher than the experimental rate coefficients.