The essential role of the air void size distribution in air-entrained cementitious materials is widely accepted. However, how the air-entraining behavior is affected by features such as the molecular structure of air-entraining agents (AEAs), the type of solid particles, or the chemical environment of the pore solution in fresh mortars is still not well understood. Besides, methods to assess the interaction between AEAs and cement particles are limited. Thus, in this study, the air-entraining behaviors of three kinds of surfactant (cationic, anionic, and nonionic) were examined. The general working mechanisms of these surfactants were studied by zeta potential and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. Results indicate that the cationic surfactant entrains improper coarse air voids due to the strong electrical interaction between air bubbles formed by the cationic surfactant and negatively charged cement particles. The anionic surfactant interacts with the positively charged part of cement particles, and thus entrains finer air voids. The interaction between the nonionic surfactant and cement particles is very weak; as a result, the nonionic surfactant entrains the finest and homogeneous air voids.