Abstract: This work reported a theoretical and experimental study on the reaction kinetics of ethyl formate and the hydroxyl radical. Theoretically, accurate potential energy surface was calculated at the M06-2x/ma-TZVP level of theory. The torsional anharmonicity was then considered with the multi-structure torsion (MS-T) method and the corresponding torsional correction coefficients were obtained. The rate coefficients at 200~2 000 K were computed with transition state theory including the Eckart tunneling correction. Experimentally, a series of shock tube experiments at 900~1 321 K and 1.4~2.0 atm were conducted to measure the rate coefficients. In detail, laser absorption spectroscopy was employed to monitor the hydroxyl concentration at the absorption peak wavelength of 306.7 nm. The overall rate coefficients for the reaction of ethyl formate with hydroxyl radical were derived from the measured OH profiles based on a detailed kinetic model. Our calculations were validated against these experimental measurements, justifying the accuracy and rational of the theoretical predictions.