Recently developed technique of measuring minor species concentration by using the modulation dip in broadband CARS has been applied to the flame structure study of methane/air premixed flames in a counterflow. This method used the modulation dip from the cold band CO Q-branch resonant signal superimposed on the nonresonant background. The measured CO concentration profile in a symmetric and unsymmetric methane/air premixed flames together with the velocity and temperature by using LDV and CARS have been compared with the numerical results adopting detailed chemistry modeling. The results show that there is a satisfactory agreement between the experimental data and numerical results for velocities, temperatures and CO concentrations. And the modulation dip technique of measuring minor species, such as CO is a viable tool for a quantitative measurement in a flame.