In order to solve the excessive air and poor bubble size distribution introduced by polycarboxylate superplasticizer, the process of “eliminating large bubbles and introducing small bubbles” was adopted. Polycarboxylate superplasticizer was compounded with different kinds of defoaming agents and air entraining agents. The synergistic compatibility between polycarboxylate superplasticizer, defoaming agents and air entraining agents was studied by taking air content, fluidity, compressive strength and pore structure parameters of the mortar as indicators. The results show that the defoaming agent can significantly reduce the content of inferior bubbles introduced by polycarboxylate superplasticizer, and improve the strength, as well as reduce the fluidity of mortar. The air entraining agent can increase the bubble content in the diameter range of 10300μm, and reduce the negative influence of the defoaming agent on the fluidity to improve the working performance of the mortar. Therefore, the process of “eliminating large bubbles and introducing small bubbles” can improve the compressive strength while maintaining the fluidity of mortar.