Enhancement in dispersion of polycarboxylate superplasticizer (PCE) could be obtained by incorporating retarders in normal concrete. The generally believed reason was that the consumption of free water and polymer at the beginning was reduced by retarding cement hydration. This theory could not convincingly explain why sodium hexametaphosphate (SHMP) was able to promote the dispersion capacity of PCE, while trisodium phosphate (TSP) could not, despite that both TSP and SHMP could obviously retard the cement hydration. The adsorption behavior of PCE and phosphate was investigated and the mechanism was analyzed in order to gain deeper understanding. The results showed that TSP and SHMP delayed the cement hydration, impeded adsorption process of PCE, and increased thickness of adsorption layer. It was interesting that TSP reduced the dispersion, but SHMP enhanced. The reason for this contradiction was due to the difference in composition of adsorption layer. In the PCE-TSP system, this layer was composed of the precipitates (formed by TSP and Ca2+) and the invalided PCE (caused by these precipitates in the immediate vicinity of the cement grains); the invalided PCE was due to the decrease of PCE dispersion. In the PCE-SHMP system, “Inner-phosphate (multi-layers) + Outer-PCE (single layer)” structure was formed to make the PCE work more effective, hence enhancing the dispersion. These results were expected to be useful for the design of highly efficient dispersants.