The present study evaluates the effect of the cationic initiator on the hydrodynamic diameter of copolymers of N-isopropylacrylamide nanogels synthesized via a surfactant-free precipitation polymerization at 70 °C in the presence of the cationic initiator 2,2'-azobis[2- methylpropionamidine] dihydrochloride. Three types of polymeric nanoparticles were synthesized using N, N'-methylenebisacrylamide as a crosslinker. The first batch was used as a reference. The second type of particles included a poly(ethylene glycol) methyl ether-acrylate monomer, while the third type used an N-tert-butylacrylamide comonomer. The hydrodynamic diameters of the synthesized particles were between 160 and 970 nm at 18 °C. The chemical composition and morphology of the synthesized co-polymeric nanoparticles were confirmed using infrared spectroscopy, nuclear magnetic resonance and scanning electron microscopy. The zeta potentials measured via dynamic light scattering were 20.0, 17.0, -0.1 mV for the three types, respectively. The volume phase transition temperature was between 22 and 41 °C. The polydispersity index of particles synthesized with N-tert-butylacrylamide varied depending on the measurement temperature.