Due to its large volume and poor thermal conductivity, mass concrete is prone to temperature cracking caused by heat release during cement hydration after pouring. To address the issue of temperature cracking in mass concrete, this study utilized emulsion polymerization to prepare polybutyl acrylate (PBA) emulsions. At an optimal dosage of 1.5%, the addition of a PBA emulsion reduced the temperature rise of cement paste by 12.4%. The inhibitory mechanism of a PBA emulsion on cement hydration was analyzed by characterization techniques such as isothermal calorimetry, X-ray diffraction Rietveld full-profile fitting method (XRD), thermogravimetric–differential scanning calorimetry (TG-DSC), and mercury intrusion porosimetry (MIP). The results showed that the C3S content in the cement specimens with 1%, 1.5%, and 2% PBA increased by 13.83%, 23.52%, and 34.65% compared to the blank group, respectively, while the C3A content increased by 92.59%, 79.63%, and 96.30%, respectively. The addition of a PBA emulsion can slow down the hydration rate of C3S and C3A, thereby reducing the temperature rise and fall rate of cement hydration, reducing the peak heat release of the hydration reaction, and ultimately achieving the inhibition of the cement hydration reaction. In addition, the mechanical properties of PBA-modified cement-based materials were also tested. The results show that the addition of PBA can affect the early strength development of cement samples, but has no effect on the strength after 60 days. Therefore, PBA can be used as a hydration temperature rise control material to reduce the risk of temperature cracking in mass concrete.