The salinity of seawater can affect the properties of mixtures of polycarboxylate superplasticizer (PCE) and seawater. The purpose of this research is to study the effect of different salinities of water on the property of seawater-mixed cement slurry. Two PCE types with different side chain lengths and acid–ether ratios were used. Their physicochemical properties were explained by nuclear magnetic resonance (NMR), size exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR), turbidimetry, and dynamic light scattering (DLS) analysis. The performance of the PCEs was measured using slump, rheological energy, and solidification time. Finally, by measuring the adsorption volume, adsorption layer thickness, and water film thickness (WFT), the mechanisms involved in performance modification were studied. The results show that the workability and rheological performances of seawater-mixed cement paste are decreased by increasing salinity. With the increase in salinity, the minislump of the seawater-blended cement pastes with two PCEs decreased from 285 mm to 120 mm and from 280 mm to 78 mm, respectively, and the thixotropic areas were increased from less than 2000 Pa/s to above 10,000 Pa/s. Moreover, the adsorption amount of the two PCEs in the cement mixed with high-salinity seawater decreased by 55.99% and 71.56%, respectively, and the thickness of the adsorption layer and water film was decreased with increasing salinity. Compared with the two PCEs, PCE with long side chains and a high acid–ether ratio provided better salt resistance.