A novel quantitative optical diagnostics method for determining the threshold of soot onset in counterflow diffusion flames was proposed and demonstrated. The method was based on the proportional discrimination of trichromatic luminescence and the nonparametric and unsupervised automatic threshold selection algorithm. The macroscopic soot onset threshold in ethylene diffusion flame with three ethyl esters additions could be precisely determined. It was found that the undesirable soot onset phenomenon for ethylene diffusion flames was significantly suppressed with ethyl ester addition. The method proposed here will be useful as a reference for soot diagnostics in other flames.