An experimental study has been carried out on the synthesis of carbon nanomaterials using Ni catalyst in methane / air laminar, fuel-rich premixed flames under atmospheric pressure. By placing a pair of porous media in the upstream and downstream sides of the combustion space, excess enthalpy burning was applied to the methane / air mixture. We have investigated effect of reaction time on nanomaterials growth. As a result, it has been clarified that carbon nanomaterials with a diameter of from 20 to 50 nm are synthesized in the downstream side of the exothermic reaction zone.