A Single pulse shock tube was used to investigate the thermal decomposition of ethyl formate over the temperature range of 909–1258 K and pressure range of 9–17 atm. RRKM (Rice‐Ramsperger‐Kassel‐Marcus) theory was used to estimate the temperature (500–2500 K) and pressure dependent (0.01–100 atm) rate coefficients. The products identified were methane, ethylene, and propane. The initial elementary step for the decomposition of ethyl formate is the unimolecular elimination of ethylene via the reaction CH3CH2OC(O)H → CH2=CH2 + HCOOH. The formed formic acid is further decomposed within the studied temperature range. A detailed reaction mechanism proposed with 21 species and 22 elementary reactions was used to simulate reactant and product distribution over the investigated temperature range. The temperature dependent rate coefficient for the total decomposition of ethyl formate was found to be (909–1258 K)=2.68 × 1011 (s−1) exp (‐42.9 ± 2.2 kcal mol−1/RT). The bond dissociation energies were calculated for the various types of bonds. The calculated total rate coefficient for the thermal decomposition of ethyl formate is (500–2500 K)=3.61 × 1013 (s−1) exp (‐53.4 kcal mol−1/RT) at high pressure limit.