By applying a novel approach to evaluate photofragmentation laser-induced fluorescence (PFLIF) imaging, experimental quantitative information on the temporal in-cylinder distribution of hydrogen peroxide (H2O2) in a homogeneous charge compression ignition (HCCI) engine was extracted. The results from PFLIF were then compared to those obtained from chemical kinetics simulations using computational fluid dynamics (CFD) and a stochastic reactor model (SRM). For the CFD simulations, a sector mesh was applied using Reynolds-averaged Navier-Stokes (RANS) equations together with a reduced chemical kinetic model. These simulations provided detailed information on the spatial distribution of H2O2, HO2 as well as other important species and temperature. The SRM, which offers substantially reduced simulation times but no spatial information, was used with the same reduced kinetic model. Two-dimensional images from PFLIF and CFD show a fair temporal agreement, while details of the spatial distributions disagree. The CFD images show that the combustion chemistry is affected by the interaction with the cylinder walls with, for instance, a local delay of the formation and consumption of H2O2. By using probability density functions (PDFs) of H2O2 and HO2 mass fractions, comparisons could be made between experimental data and both the CFD and SRM simulations. In general the range of mass fractions show good agreement but the experimental distributions are wider. Possible reasons for this discrepancy are actual heterogeneities in the H2O2/HO2 concentration distributions not predicted by the model, spatial temperature variations, which will influence the strength of the PFLIF signal, spatial variations in the laser profiles, not accounted for in the data processing, and photon noise. The good agreement between the CFD and SRM shows the relevance of fast PDF based simulation tools. (C) 2015 The Combustion Institute. Published by Elsevier Inc. All rights reserved.