The triblock Pluronic F127 was modified by introducing poly(N-isopropylacrylamide) (PNIPAM) at both the poly(ethylene oxide) ends, and the pentablock copolymer so-prepared was characterized by gel permeation chromatography and ¹H NMR. The degree of polymerization of NIPAM blocks at the two ends was 7. The solution behavior and microstructure of copolymer aggregates in water and aqueous salt solution were examined and compared with F127 by UV–visible absorption spectroscopy, microdifferential scanning calorimetry, dynamic light scattering (DLS), and small-angle neutron scattering (SANS). The behavior of the pentablock copolymer at the air/water interface was determined by Langmuir film balance. Two lower critical solution temperatures were observed for pentablock copolymer, corresponding to poly(propylene oxide) and PNIPAM blocks, respectively. DLS studies show that micelle size increased with increase in temperature and in the presence of salt. SANS measurements provided temperature-dependent structural evolution of copolymer micelles in water and salt solution. The copolymer displays an isotherm with four classical regions (pancake, mushroom, brush, and condensed state). The study has potential applications in controlled drug delivery due to the tunable phase behavior and biocompatibility of the copolymer.