Dibutyl ether (DBE) is a promising biofuel due to its high cetane number (~ 100) and high volumetric energy density (31.6?MJ/L). It could either be used directly in compression ignition engines or blended with other conventional or renewable fuels. Oxidation and pyrolysis kinetics of DBE are not well known, particularly at high pressures. In this work, we have experimentally investigated the chemical kinetics of DBE in three domains: (a) ignition delay time measurements in a rapid compression machine over T?=?550–650?K, P?=?10, 20, 40?bar, ??=?0.5, 1; (b) ignition delay time measurements in a shock tube over T?=?900–1300?K, P?=?20, 40?bar, ??=?0.5, 1; (c) laser-based carbon monoxide speciation measurements in a shock tube during DBE pyrolysis and oxidation over T?=?1100–1400?K, P?=?20?bar. Pressure time-histories measured in RCM experiments exhibited unique 3-stage and 4-stage ignition behavior predominantly at fuel-lean conditions. Experimental data were compared with the predictions of two recent chemical kinetic models of DBE. Sensitivity analyses were carried out to identify key reactions which may have caused the discrepancy between experiments and simulations. It was found that the rate of decomposition of DBE may need to be revisited to improve the oxidative and pyrolytic predictions of DBE kinetic model.