The cement dispersion performance of a polycarboxylate (PCE)-based superplasticizer is highly related to their adsorption behaviors as a function of time. This study evaluated effects of PCEs on rheological properties of cementitious materials. First, characteristics of PCEs were characterized via permeation chromatography (GPC) and Fourier-transform infrared spectrometry (FT-IR). The adsorption behavior of single and blended PCEs on cementitious composites was identified using total organic carbon analyzer (TOC). Based on the measurement of PCE adsorption, the changes of rheological properties of cementitious materials as well as the number of dispersed cement particles were characterized using a rheometer and laser spectroscopy, respectively. The experimental results support the systematic mechanism of PCE adsorption, cement dispersion, and the decrease in viscosity of cementitious materials.