In this study, the synthesis of small molecules and use of an improved “one-pot” method to synthesize the reversible addition–fragmentation chain transfer polymerization (RAFT) reagents have been reported. By comparing with the RAFT reagents synthesized by the traditional “step-by-step” method, it was observed that the reagents synthesized by the two methods had the same structure, however, the improved “one-pot” preparation method results in a significantly higher yield. Subsequently, two different macromolecular CTA segments (PVP-CTA-PVP and PDMAEMA-CTA-PDMAEMA) were prepared by RAFT polymerization, followed by the synthesis of the block polymer PDMAEMA-b-PVP-CTA-PVP-b-PDMAEMA. Through FITR, NMR, GPC and DLS analysis of the block polymer, it was observed that the isotacticity gradually became dominant as the degree of polymerization increased. Further, using NMR spectroscopy to study the effect of pH on the block polymer, the ionization degree of the synthesized polymer in the tumor tissue environment was observed to range between 86.32% to 99.50%, which proved that the synthesized polymers exhibit significant prospects in the medical application.