Two different groups of comb-like copolymer dispersants with side chain lengths ranging from 8 to 48 were synthesized and characterized: one group with the carboxylic content per mole molecule constant and the other group with the carboxylic contents per gram polymer constant. The effects of side chain length on comb-like copolymers on adsorption, dispersion, rheological behavior, and zeta potential for cement suspensions were investigated systematically to elucidate the governing dispersing mechanism. The adsorption of comb-like copolymer on the cement surfaces, controlled by COO(-) content in copolymer backbones, side chain length, and also polymer conformation in solution, governs the dispersion and rheological behavior of the cementitious system. The dispersion effect increases with the adsorbed amount; especially the adsorbed side chain density increases. But the dispersion power of comb-like copolymers varies depending on the side chain length in comb-like copolymer. The long side chain polymer has higher dispersion power than the shorter ones due to the stronger steric hindrance effect of the former; for the short side chain polymer with high ionic content, the electrostatic repulsion and steric hindrance together should be responsible for its dispersion effect. Such information also suggests that their exists the geometrical balance between the main chain and the side chains in comb-like copolymer dispersants which should be very useful in designing optimum molecular structures of high efficient dispersants.