In this study, three hydration heat controlling materials (HHCMs), respectively, containing pure hydroxyl (polyvinyl alcohol, PVA), carboxylic (polyacrylic acid, PAA) and ester groups (maleic acid-ethylene glycol ester, P(MA-EG)) were synthesized and mixed with cement-based materials, and the hydration heat and setting time of cement pastes and the SEMI adiabatic temperature rise and strength of mortars were tested. The results showed that PAA and P(MA-EG) reduced the peak value of hydration exothermic rate by 77.45% and 62.28%, respectively, and prolonged 54.14 h and 15.56 h, respectively. Mechanism studies showed that HHCMs containing carboxylic or hydroxyl groups adsorbed on cement particles by Ca2+ complexation, while HHCMs containing ester groups hydrolyzed to carboxylic groups in alkaline cement pastes, which hydrolysis rate changed with the hydration temperature of cement-based materials to regulate the hydration process. This study aims to provide technical feasibility and theoretical basis for exploring new avenues of synthesizing HHCMs with different functional groups.