Abstract Ignition delay times of the three C5 primary alcohol isomers (n-pentanol, iso-pentanol and 2-methyl-1-butanol) were measured behind reflected shock waves. Experiments were conducted in the temperature range of 1100–1500 K, pressures of 1.0 and 2.6 atm, equivalence ratios of 0.25, 0.5 and 1.0, and O2 concentration in the fuel/O2/Ar mixtures varying from 3.75% to 15%. Measurements show that the ignition delay time and the global activation energy of the three isomers both decrease in the order of iso-pentanol, 2-methyl-1-butanol, and n-pentanol. Chemical kinetic mechanisms for n-pentanol (Mech NP) and iso-pentanol (Mech IP), recently developed by Dagaut and co-workers, were used to model the respective ignition delay times. Results show that Mech NP yields close agreement at the equivalence ratio of 0.25, but the agreement is moderated with increasing equivalence ratio. Mech IP yields fairly close agreements at relatively higher temperatures but over-predicts the measurements by 50% at relatively lower temperatures for the three equivalence ratios studied. A new 2-methyl-1-butanol high temperature mechanism was proposed and validated against the ignition delay data. Sensitivity analysis for both n-pentanol and iso-pentanol showed the dominance of small radical reactions. Reaction pathway analysis aided further scrutiny of the fuel-specific reactions in Mech NP, leading to refinement of the kinetic model, and improved agreement between the predicted and measured ignition delay times as well as the jet-stirred reactor results.