A series of polycarboxylate superplasticizers (PCEs) with different side-chain densities, main chain polymerization degrees, and side-chain lengths were designed and synthesized using a novel highly active ethylene glycol mono vinyl ether polyethylene glycol as the ether monomer. The influence of polycarboxylate ether on the rheological properties, interface adsorption, and hydration characteristics in cement paste was investigated through characterization of charge density, rheological properties, adsorption behavior, and hydration heat. The results indicate that the adsorption process of PCE on cement particles is spontaneous physical adsorption, and the hydration kinetics fitting reveals that the geometric crystal growth exponent n is in the range of 1–2, with needle-like and lamellar hydration products formed. With a decrease in side-chain density, the broadening of molecular weight distribution and the increase of charge density accelerate the flow of slurry, reduces saturation adsorption, and delays cement hydration. A decrease in main chain polymerization degree results in a downward trend in molecular weight and charge density, leading to larger molecular conformations, reduced slurry flow, decreased saturation adsorption, and delayed cement hydration. As the side-chain length of PCE (molecular weight) increases, the charge density decreases, and the molecular conformation exhibits a compact structure with reduced slurry flow, decreased saturation adsorption, and delayed cement hydration. In cases of low side-chain density, short side chains, and low molecular weight, enhanced adsorption capacity and faster adsorption rates are observed, resulting in the lower viscosity and a delay in the cement hydration process.