To get a better understanding of low temperature oxidation chemistry of tong-side-chain cycloalkanes, the low- and intermediate-temperature oxidation mechanisms and kinetics of ethylcyclohexane (ECH) have been investigated by using a combination of electronic-structure theory, transition state theory (TST) and Rice-Ramsberger-Kassel-Marcus/Master-Equation (RRKM/ME) theory in this work. The high pressure limit rate constants for reactions with tight transition states are obtained by the TST, while the high pressure limit rate constants for barrierless reactions are obtained by the variational transition state theory (VTST). The rate constants in the fall-off range for pressure-dependent reactions are obtained by RRKM/ME theory. Depending on the position of the extracted H atom on the ring or on the side chain, the oxidation of ECH is mainly initiated by H-abstraction with OH radical to form cyclic C8H15 radicals having six isomers (R1-R6) at low (500-900 K) and intermediate (900-1100 K) temperature and in this study we focus on the kinetics of the reactions starting from these isomers. At low temperature, it is shown that, for addition reactions of O-2 to cyclic C8H15 radicals, the calculated rate constants when the unpaired electron of the radicals is in the side-chain are smaller than when in the ring. The intramolecular isomerization reactions of six cycloalkylperoxy radicals (R1OO-R6OO) by H-shift can lead to a large number of hydroperoxycycloalkyl radicals (QOOH) and it is shown that the 1,5 H-shift is more competitive than the 1,6 H-shift in the R1OO-R6OO. Furthermore, unimolecular elimination reactions of QOOH can form OH, HO2, cyclic ethers, ketones, aldehydes and conjugated olefins. The calculated results indicate that the formation cyclic ethers of ECH oxidation are inclined to 1-oxaspiro[3,5]octane, 8-methyl-7-oxa-bicyclo[4.2.0]octane, 7-methyl-6-oxa-bicyclo[3.2.1]octane and 2-ethyl-6-oxa-bicyclo[3.1.1]heptane. At intermediate temperature, the most important reaction type of R1-R6 consumption is the C-C bond fission to form smaller products. The reaction pathways and potential energy surfaces to form the main products (ethylene, butadiene, 1-butene, and so on) of R1-R6 decomposition are also performed and the rate constants of the corresponding reactions are calculated by using the TST. Rate constants of these reactions are fitted by a nonlinear least-squares method to the form of a modified Arrhenius rate expression, which can be directly used for the modeling study of low temperature oxidation of cycloalkanes. (C) 2015 The Combustion Institute. Published by Elsevier Inc. All rights reserved.