In this study, the effect of both main and side chain length changes of the admixtures on some properties of cementitious systems were investigated. Three different polycarboxylate-ether-based water-reducing admixtures (WRA) having constant molecular weights and different main and side chain lengths were synthesized. Single type of raw material and carboxylate functional group were used in all WRAs. The molecular weights, free nonionic contents, and anionic/nonionic ratios of the admixtures were kept constant. Test results showed that degree of fluidity was observed in cement paste and mortar mixtures in case the admixture main and side chain length is more or less than a critical value. This negative effect is thought to be due to the weakening of the adsorption ability by the chain length change of the admixtures, the being tendency of polymers to intertwine and the adsorbing of admixture on several cement particles simultaneous. Admixtures having excessive long or short main chain and side chain improved the time-dependent slump-flow retention of the mortar mixtures. The admixtures with short main and side chains had insufficient adsorption ability and the admixture with excessive long main and side chains had the interlacing risk of polymers. In both cases, time-dependent behavior improved because the amount of free admixture in solution increased. The change in the chain lengths of the WRAs affected the 1-day compressive strength of the mortar mixtures.