Six derivatives of poly--vinylcaprolactam (PNVCL) P1-P6 were synthesized via surfactant-free precipitation polymerization (SFPP) at 70 °C, with potassium persulfate (KPS) as the initiator. P5 and P6 were synthesized using the cross-linker ,'-Methylenebisacrylamide (MBA). The conductivity was measured to monitor the polymerization process. The hydrodynamic diameters (HDs) and polydispersity indexes (PDIs) of aqueous dispersions of P1-P6 were determined using dynamic light scattering (DLS) and zeta potential (ZP) using electrophoretic mobilities. At 18 °C for P1-P6, the HDs (nm) were 428.32 ± 81.30 and PDI 0.31 ± 0.19, 528.60 ± 84.70 (PDI 0.42 ± 0,04), 425.96 ± 115.42 (PDI 0.56 ± 0.08), 440.34 ± 106.40 (PDI 0.52 ± 0.09), 198.39 ± 225.35 (PDI 0.40 ± 0.19), and 1201.52 ± 1318.05 (PDI 0.71 ± 0.30), the and ZPs were (mV) 0.90 ± 3.23, -4.46 ± 1.22, -6.44 ± 1.82, 0.22 ± 0.48, 0.18 ± 0.79, and -0.02 ± 0.39 for P1-P6, respectively. The lower critical solution temperature ranged from 27 to 29 °C. The polymers were characterized using the ATR-FTIR method. The study concluded that the physicochemical properties of the product were significantly affected by the initial reaction parameters. Polymers P1-P4 and P6 have potential for use as drug carriers for skin applications.