Measurements of the rate constant for the reaction of OH radicals with propionaldehyde as a function of temperature were performed using low-pressure discharge-flow tube techniques coupled with laser-induced fluorescence detection of OH radicals. The measured room-temperature rate constant of (1.51 +/- 0.22) x 10(11) cm(3) molecules(-1) s(-1) at 4 Ton was generally lower but in reasonable agreement with previous absolute and relative rate studies at higher pressures. Measurements as a function of temperature resulted in an Arrhenius expression of (2.3 +/- 0.4) X 10(-11) exp[(-110 +/- 50)/T] cm(3) molecules(-1) s(-1) between 277 and 375 K at 4 Torr. The observed temperature dependence at low pressure is in contrast to previous measurements of a negative temperature dependence at higher pressures. Ab initio calculations of the potential energy surface for this reaction suggest that the primary reaction pathway involves the formation of a hydrogen-bonded prereactive complex, which could account for the difference in the observer' temperature dependence at lower and higher pressures.