Autoignition experiments of stoichiometric mixtures of s-, t-, and i-butanol in air have been performed using a heated rapid compression machine (RCM). At compressed pressures of 15 and 30 bar and for compressed temperatures in the range 715-910 K, no evidence of a negative temperature coefficient region in terms of ignition delay response is found. The present experimental results are also compared with previously reported RCM data of n-butanol in air. The order of reactivity of the butanols is n-butanol > s-butanol ≈ i-butanol > t-butanol at the lower pressure but changes to n-butanol > t-butanol > s-butanol > i-butanol at higher pressure. In addition, t-butanol shows preignition heat release behavior, which is especially evident at higher pressures. To help identify the controlling chemistry leading to this preignition heat release, off-stoichiometric experiments are further performed at 30 bar compressed pressure, for t-butanol at φ = 0.5 and φ = 2.0 in air. For these experiments, higher fuel loading (i.e., φ = 2.0) causes greater preignition heat release (as indicated by greater pressure rise) than the stoichiometric or φ = 0.5 cases. Comparison of the experimental ignition delays with the simulated results using two literature kinetic mechanisms shows generally good agreement, and one mechanism is further used to explore and compare the fuel decomposition pathways of butanol isomers. Using this mechanism, the importance of peroxy chemistry in the autoignition of the butanol isomers is highlighted and discussed. © 2013 American Chemical Society.