Temperature-sensitive poly(N-isopropylacrylamide) (PNIPAM) microgels with sulfate, amidino, or carboxylic groups on their surfaces, were synthesized by precipitation polymerization based on ammonium persulfate (APS), 2,2'-azobis(amidinopropane) dihydrochloride (V50), or 4,4'-azobis(4-cyanovaleric acid) (ACVA) as initiator, respectively. Their particle sizes and swelling ratios depended on the reaction pH due to the pH dependence of the ionization degree of the decomposed fragments originating from the initiators and their hydrophilicity-hydrophobicity. The more hydrophobic initiators partitioned into the interior of the PNIPAM microgels under certain pH conditions initiated the crosslinking reaction between the PNIPAM chains, leading to higher crosslinking density of the microgels resulting in their smaller swelling ratio. pH dependence of surface charge density of the microgels with amidino groups or carboxylic acid groups on their surfaces was evidenced by the variation of their potentials as a function of pH. Correspondingly, due to their pH dependence of electrostatic repulsive effect, the colloidal stability of the microgels with amidine groups or carboxylic acid groups on their surfaces was dependent on the pH value of dispersion medium. (c) 2006 Wiley Periodicals, Inc.