The lower critical solution temperature (LCST) behaviors of random and segmented copolymers of N-isopropylacrylamide (NIPAM) and acrylic acid (AA) prepared in dioxane and water have been investigated by using ultrasensitive microcalorimetry (US-DSC). The introduction of AA increases the LCST of the former but slightly affects that of the latter. When the molar fraction of AA is low (similar to 2 mol %), the LCST of the segmented copolymer shifts to a higher temperature with increasing pH, while the LCST of the corresponding random copolymer slightly changes. Below the boiling point of water, the random copolymer and segmented copolymer with the molar fraction of AA about 15 mol % no longer exhibit an LCST at pH > 5. The addition of calcium ions leads the LCST of both the segmented copolymer and random copolymer to decrease. Our results suggest that the LCST behavior of the copolymers is determined by the clustering of poly( N-isopropylacrylamide) segments.