The ozone (O-3) decomposition in the pre-heat zone of flames can initiate and accelerate the chain-branching reactions. In the present study, formaldehyde (CH2O) was investigated by both experiment and simulation methods in methane/air laminar premixed flames under atmospheric conditions. The formaldehyde concentration profiles in the flames were measured with CH2O-PLIF. When 4500 ppm of ozone was added, the formaldehyde concentration in Bunsen type laminar flame was enhanced by 58.5% at fuel-rich condition (phi = 1.4) and 15.5% at stoichiometric condition. In the simulation work, the most recent ozone sub-mechanism was coupled with GRI-mech 3.0 kinetic mechanism. It showed that with 4500 ppm ozone addition, the formaldehyde concentration was enhanced by about 48.1% at rich condition (phi = 1.4) and about 14.7% in stoichiometric mixture. The simulation suggested an early production of CH2O with ozone addition, especially in rich conditions. These reactions occurred at relatively low temperature, around 500 K. In order to isolate these reactions from the flame, experiments with pre-heated unburned mixtures were carried out. A larger amount of formaldehyde was produced in the zone far from the flame as the preheating temperature was increased. It indicated that the combustion enhancement with ozone could be caused by the additional reactions of ozone at relatively low temperature. Simulations showed that methoxy radical (CH3O) is the key specie for production of formaldehyde at lower temperatures. Early in the pre-heat zone of the laminar flame, formaldehyde occurs via decomposition of CH3O while in the pre-heated gas mixture via reaction of CH3O with O-2. Furthermore, the O-3 effect on turbulent flames was investigated showing a greater enhancement in formaldehyde signal than that in the laminar cases. This difference in formaldehyde signal enhancement could be attributed to the expansion of the preheat zone, due to turbulence. (C) 2014 The Combustion Institute. Published by Elsevier Inc. All rights reserved.