During shield construction in underground spaces, synchronous grouting slurry is poured between the surrounding rock and tunnel lining to ensure stability. For synchronous grouting slurries, few studies have investigated the relationship between the rheological parameters and physical properties, grout-segregation mechanism, and anti-segregation performance. Therefore, we explored the relationships between the slurry rheological parameters, segregation rate, and bleeding rate. Cement, sand, fly ash, and bentonite were used to prepare the slurry, and the effects of different polycarboxylate water-reducing agents and dispersible latex powder dosages were studied. The rheological parameters of 16 groups of uniformly designed slurries were tested, and the data were fit using the Herschel–Bulkley model. The optimal mix ratio lowered the slurry segregation rate, and its rheological behaviour was consistent with the Herschel–Bulkley fluid characteristics. High-yield-shear-stress synchronous grouting slurries with high and low viscosity coefficients were less likely to bleed and segregate, respectively. The optimised slurry fluidity, 3 h bleeding rate, 24 h bleeding rate, segregation rate, coagulation time, and 28 days compressive strength were 257.5 mm, 0.71%, 0.36%, 3.1%, 6.7 h, and 2.61 MPa, respectively, which meet the requirements of a synchronous grouting slurry of shield tunnels for sufficiently preventing soil disturbance and deformation in areas surrounding underground construction sites.