In this work, we establish a quantitative relationship between the fluorescence signal intensity of acetone and toluene and their concentration, and acetone/toluene planar laser‐induced fluorescence (PLIF) is developed to measure the concentrations of two components simultaneously, providing an equivalent ratio distribution of the flow field. Due to a thorough consideration of the tracer effect on each other's fluorescence signals, the uncertainty in the PLIF concentration measurement is reduced to 10.4%. Experimental results of OH‐PLIF and acetone/toluene PLIF indicate that the equivalence ratio distribution obtained by acetone/toluene PLIF in cold‐state flow fields can be employed to predict and analyze the trend of equivalence ratio distribution in the combustion field.