Concrete is vital for the development of modern buildings. However, they suffer from the high viscosity problem in their application process due to the use of a low water–cement ratio in order to maintain their high strength. Developing PCEs with the presence of ester functional groups in their molecular structure is one of the most effective measures to improve the flowability of concrete. Here, three PCEs with different alkyl densities of acrylic acid ester: PCE-M, PCE-E, and PCE-B were designed to explore their viscosity-reducing effect on the performance of cement and concrete. The structures of the three PCEs were characterized via Fourier transform infrared (FTIR) spectra, proton nuclear magnetic resonance (1H NMR), and gel permeation chromatography (GPC). Their properties were also determined via zeta potential, surface tension, and rheological experiments. It was found that PCE-M had the best performance, with the lowest surface tension, highest zeta potential, and therefore highest charge density on the cement particles, lowest viscosity, and highest flowability of cement paste, and exhibited the best performance of concrete in terms of workability. The best performance of PCE-M in reducing the viscosity of cement and concrete can be ascribed to the smallest amount of water-repellent alkyl groups, enhancing the electrostatic repulsion and reducing the viscosity, thereby boosting the dispersion and stabilization of cement pastes and concrete. This study shed lights on designing other PCEs with high viscosity-reducing effects via an ester group control.