Poly(N‐isopropylacrylamide)‐block‐poly(l ‐lactic acid)‐block‐poly(N‐isopropylacrylamide) (PNIPAAM‐b‐PLLA‐b‐PNIPAAM) and PNIPAAM‐b‐PDLA‐b‐PNIPAAM triblock copolymers with varying polylactic acid (PLA) lengths are synthesized using a combination of ring‐opening polymerization and atom‐transfer radical polymerization. Results of 1H NMR and gel permeation chromatography analyses show that the copolymers have a well‐defined triblock structure and the PLA segment lengths can be readily controlled with monomer feed ratio. Stereocomplexation between the enantiomeric PLA segments is confirmed with differential scanning calorimetry and wide‐angle X‐ray scattering. Dynamic light scattering experiments show that (1) the LCST of PNIPAAM in water could be tailored from 32 °C up to 38.5 °C by increasing the length of PLA segments and mixing copolymers of similar molecular weight with enantiomeric PLA segments to induce stereocomplexation, and (2) the LCST of each mixed copolymer system could be tailored within a 2–3 °C range of body temperature by manipulating the ratio of the enantiomeric copolymers in solution.
