The rate coefficient for the gas-phase reaction of OH radical with α-pinene was measured at 298 K using relative rate methods, with propylene as a reference compound. The ratio of the rate coefficient for the reaction of OH radicals with α-pinene to that of with OH radicals with propylene was measured to be 1.77 ± 0.21. Considering the absolute value of the rate coefficient of the reaction of OH radicals with propylene as (3.01 ± 0.42)×10−11 cm3 molecule−1 s−1, the rate coefficient for the reaction of OH radicals with α-pinene was determined to be (5.33 ± 0.79)×10−11 cm3 molecule−1 s−1. To gain a deeper insight into the reaction mechanism, theoretical calculations were also carried out on this reaction. The rate coefficient of OH radical with α-pinene was calculated using canonical variational transition state theory with small-curvature tunnelling. The kinetics data obtained over the temperature range of 200–400 K were used to derive the Arrhenius expression: k(T) = 3.8×10−28 T5.2 exp[2897/T] cm3 molecule−1 s−1. The OH-driven atmospheric lifetime (τ) and ozone formation potential of α-pinene were calculated and reported in this work.