A series of thermally responsive copolymers of N-isopropylacrylamide (NIPAAM) with a fluorinated hydrophobic comonomer, either hexafluoroisopropylmethacrylate (HFIPMA) or 2,2,3,3,4,4-hexafluorobutylmethacrylate (HFBBMA) and a hydrophilic comonomer, methacrylic acid (MAA), were synthesized by emulsion polymerization. The chemical structures of the copolymers were studied by the IR technique. Dynamic light scattering (DLS) showed that aqueous latices of the copolymers exhibited swelling-deswelling changes typical to PNIPAAM; the degree of swelling as well as the temperature at which the polymers collapse depended on the chemical structure of the comonomers. Endotherms related to the contraction of the polymers were studied by differential scanning calorimetry (DSC). A combination of DLS and DSC results revealed that the hydrophobic and hydrophilic units in the copolymers strongly affected the swelling behavior, as well as the local environment of the PNIPAAM chains. The comonomer HFIPMA increased the hydrophobicity of NIPAAM, reduced the swelling, and caused coagulation of the copolymer of NIPAAM and HFIPMA at temperatures above the critical temperature. Hydrophobicity of HFIPMA also affected the rheological properties of the latex. The HFBMA comonomer increased the swelling of the latex particles. Methacrylic acid added into the associating copolymers made the copolymers to show polyelectrolyte behavior with an increase of swelling and a decrease of the enthalpy change upon the collapse.