This study investigates the synthesis and characterization of polycarboxylate ether-based superplasticizers (PCE-based SPs) used in concrete. The PCE-based SPs were synthesized using methacrylic acid, methoxy polyethylene glycol methacrylate, thioglycolic acid, and ammonium persulfate through free radical copolymerization mechanism. Various analytical methods, including specific gravity, solid content, FT-IR, 1HNMR, GPC, TG, and XRD, were employed to characterize the prepared PCE-based SPs. The microstructure of hydrated cement pastes was examined using XRD and SEM. The impact of the chemical composition of the polycarboxylates on the rheological properties of grout mixes and the performance of the superplasticizers was evaluated through slump, flow table, and compression tests on different grout mixtures. The formulated superplasticizers demonstrated effective dispersal properties and excellent slump performance. Notably, the PC-4 mix achieved a maximum flow of 230 mm in the flow table test at a water-cement ratio of 0.25, and it exhibited high compressive strength values after 28 days of curing. XRD and SEM analysis indicated that the PC-4 hydrated paste had a denser and more compact structure, attributed to the formation of excessive hydration products compared to the neat OPC paste.