The flow reactor pyrolysis of n-pentanol at 30, 150, and 760 Torr and laminar premixed flames of n-pentanol with equivalence ratios of 0.7 and 1.8 at 30 Torr are investigated using the synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). The pyrolysis products and flame species are identified and the mole fraction profiles are measured. A detailed kinetic model of n-pentanol is developed and validated on the new experimental results. The C-C bond dissociation reactions play a significant role in the pyrolysis of n-pentanol. The contribution of the water elimination reaction becomes less important in the pyrolysis of n-pentanol than in the pyrolysis of n-butanol. Olefins and CnH2nO species are found to be the two major product families in the pyrolysis and combustion of n-pentanol, and specific products are also observed for most of the H-atom abstraction reactions of n-pentanol. The model is further validated on the experimental data of n-pentanol combustion in literature, including the species profiles in jet-stirred reactor oxidation, the laminar flame speeds and ignition delay times. (C) 2015 The Combustion Institute. Published by Elsevier Inc. All rights reserved.