The potential toxicity towards human kidneys of hemoglobin (Hb), when used directly, has severely limited its application as a red blood cell substitute and in cancer treatments. In this work, a novel hemoglobinpolymer conjugate was prepared by a reaction between the lysine amino groups of Hb and the carboxyl groups of a copolymer, poly(N-isopropylacrylamide) grafted carboxylated dextran (HOOC-Dex-gPNIPAAm), which was synthesized by single electron transfer living radical polymerization (SET-LRP) andpost-carboxylation. The conjugate was characterized by FTIR, 1 H NMR, SDS-PAGE, DLS, fluorescence spectroscopy and TEM. Results showed it had a relatively low critical micelle concentration (CMC) and could form stable spherical nanoparticles upon heating above the LCST. The redox activity and gasbinding capacity of the Hb conjugate were subsequently confirmed by UV-vis spectroscopy, indicating the retention of Hb bioactivity after conjugation. Furthermore, dextran with different numbers of PNIPAAm chains was synthesized for comparison. It revealed that at 37 C, the temperature above the LCST, the conjugation of Hb to the copolymer Dex-g-PNIPAAm could improve the stability of Hb which increased with the number of PNIPAAm chains.