The thermal-response and mechanical properties of poly(N-isopropylacrylamide) (PNIPAm) are improved by controlling the polymer nanostructure through photopolymerization in a bicontinuous cubic lyotropic liquid crystal (LLC) template. The bicontinuous cubic nanostructure increases the rate and amount of water expelled from PNIPAm for heating above the lower critical solution temperature (LCST) relative to an isotropic PNIPAm hydrogel while maintaining the mechanical integrity of the polymer. These results could allow development of PNIPAm hydrogels with proper water uptake, deswelling kinetics, volume transition, and mechanical properties required for successful performance in a growing number of advanced biological and industrial applications.