In this research, two kinds of polycarboxylate (M-PCE and O-PCE) with the same degree of polymerization in side chains but different main chains were synthesized via a radical polymerization reaction at room temperature. Along with two commercial polycarboxylates (C-PCE-1 and C-PCE-2), their properties on adsorption, hydration, zeta potential, liquid surface tension, and flowability of cement pastes were investigated. The results showed that the adsorption of M-PCE on the surface of cement particles increased 14.1% and the adsorption rate increased 24% compared with C-PCEs. Furthermore, three polycarboxylates (O-PCE, C-PCE-1, and C-PCE-2) exhibited a delayed effect on the hydration of cement due to the shielding effect of their chain alkyl groups, meanwhile the hydration of the cementitious materials by the M-PCE was not delayed but promoted because of its incomplete hydrolysis of the siloxane. As a result of the higher adsorption amount, M-PCE with siloxane groups exhibited favorable effects in terms of zeta potential, liquid surface tension, and flowability of cement pastes.