In view of the disadvantages of polycarboxylic acid grinding aids, such as poor reinforcement effect and cumbersome synthesis process, a new type of polycarboxylic acid grinding aid was prepared to meet the requirements of multifunctional admixture for cement concrete. The polycarboxylate grinding aid (PC) was prepared using acrylic acid, sodium allyl sulfonate, and isoprenol polyoxyethylene ether (TPEG) as raw materials, and ammonium persulfate as initiator in the nitrogen atmosphere. The effect of PC and its compound with triethanolamine (TEA) and triisopropanolamine (TIPA) on cement particle size and strength, and hydration process and structures of hydrated products were investigated. Moreover, the grinding mechanism of grinding aids was also proposed. The results indicate that the PC has good performance in both grinding and high-efficiency water-reducing. The average particle diameter of cement was reduced by 3.65 μm when 0.03 wt% of PC was added as grinding aid. Moreover, a high initial fluidity of the cement paste, 290 mm, could be reached when 0.08 wt% of PC was added. The fluidity loss of cement paste after 30 min and 60 min was 265 mm and 260 mm, respectively. After PC compounding with TEA and TIPA, 4.07 μm and 4.7 μm of the average particle size of the cement can be reduced, respectively. Based on the investigations on the hydration rate of cement hydration, the phases, and the microstructures of the hardened slurry, it could be concluded that grinding aids can change the hydration process of cement and improve the morphologies and structures of hydration products without influence on the type of hydrated products. Note that the compounded grinding aids, such as PC with TEA or PC with TIPA, can more effectively enhance the early and late strength of cement. This shows excellent comprehensive performance. In this study, a new type of polycarboxylic acid grinding aid was prepared to meet the requirements of the versatility of cement concrete additives, and to simplify the synthesis process, reduce production costs, improve the grinding effect, and improve the performance of cement concrete.