In order to solve the problems of large loss and poor stability of grouting slurry during shield tunnel construction, three polymers of polyacrylamide (PAM), styrene-butadiene latex (SBR) and sodium carboxymethyl cellulose (CMC-Na) were selected as raw materials to develop polymer double slurry grouting material for shield tunnel. The basic properties and water dispersion resistance of polymer double slurry were measured. Combined with CT test and hydration heat test, the pore structure and hydration mechanism of different kinds of polymer double slurry were analyzed. The results show that the early retarding effect of 0. 5% (mass fraction) PAM is the most obvious, and the water dispersion resistance is the best. CMC-Na has the effect of increasing the strength growth rate in later stage. The incorporation of polymer increases the pore size, expands the pore size distribution range, and reduces the number of pores. SBR has a significant effect on the dissolution reaction of C3A, while CMC-Na plays a controlling role in the formation of C-S-H in accelerated hydration stage.