According to the principle of radical polymerization reaction, different polycarboxylates with comb structures were synthesized. With the other two commercial polycarboxylates (C-PCE-1 and C-PCE-2), the effects of all the polycarboxylates on adsorption, hydration, zeta potential, liquid surface tension, and flowability in Portland cement were determined. Compared to O-PCE and C-PCEs, the adsorption value of M-PCE increased by 14.1% and the adsorption rate increased by 24% maximum. O-PCE, C-PCE-1, and C-PCE-2 have a delayed effect on the hydration of the cementitious materials, but M-PCE does not. Due to higher adsorption amount, M-PCE with siloxane groups has an excellent comprehensive performance of zeta potential, liquid surface tension, and flowability in cementitious materials.