A series of polycarboxylate (PCE) polymers with different molar ratio between TPEG and acid ether have been synthesized through radical copolymerization. Effect of PCE with different acid ether ratio on the air entraining property and dispersing property of fresh cement paste was investigated, and effect of PCEs with different acid ether ratio on the graded bubble structure of cement mortar was also investigated. The results show that with the increase of acid ether ratio in the PCE molecule, the air entraining and dispersing property of PCE improves. When the molar ratio between acrylic acid and TPEG monomer is higher than 4∶1, the dispersing and air entraining property of PCE reaches a relatively higher value. However, further increase of acid ether ratio leads to the decrease of air entraining performance as well as dispersing capability. With the increased acid ether ratio, the adsorption capability of PCE onto the cement surface improves which results in the increased concentration of PCE on the cement particle surface and leads to the decreased interface energy between cement particles and liquid phase. The addition of PCE can significantly improve the bubble structure of cement mortar, which mainly entrains a large number of bubbles of small and medium sizes, and decreases the proportion of large size bubbles. In this way, the bubble size tends to be smaller. With the increased acid ether ratio in PCE molecule, the proportion of small bubbles in cement mortar decreases, and the large bubbles in hardened cement mortar tends to increase.