A novel class of functional poly(N-isopropylacrylamide) (PNIPAAm) hydrogels with pendent micellar structure resulting from the pending amphiphilic polymers was designed and prepared. The influence of the pendent micellar structure on the properties of the resulted PNIPAAm hydrogels was examined in terms of morphology observed by scanning electron microscopy, thermal response through differential scanning calorimetry, and deswelling/reswelling kinetics upon external temperature changes. In comparison with the conventional ones, the novel PNIPAAm hydrogels with pendent micellar structure presented improved temperature-sensitive properties, i.e., enlarged water containing capability at room temperature, as well as improved deswelling rate upon heating.