Surface potential is a key electrochemical property of colloids in the study of particle interactions. However, the specific ion effects are not involved in the existing measuring methods. In this study, approaches for the estimation of the surface potential of montmorillonite with or without consideration of the specific ion effects were explored through the montmorillonite particle aggregation in the presence of Li+, Na+, and K+ ions. The montmorillonite aggregation process exhibited remarkable specific ion effects, and the critical coagulation concentration (CCC) values show the following: Li+ (271.8 mm) > Na+ (130.8 mm) > K+ (85.04 mm). Based on the mathematic relationship between electrostatic repulsion and the van der Waals attractive interaction at the CCC, the fluctuation coefficient ß was obtained. The value of β could quantify the strength of the specific ion effects of different cations. Then, the fluctuation coefficient β was introduced into the classical method for calculating the surface potential, considering the specific ion effects. The quantificational sequence of the ionic specificity of K+ and Na+ was as follows: βK = 1.433 > βNa = 1.187. Simultaneously, the surface potential considering specific ion effects can be obtained by introducing this coefficient. Our findings provide ideas for getting reliable surface potentials of charged particles in different electrolyte environments.