The synthesis of chiral polyaniline (PANI) induced by modified hemoglobin (Hb) was profoundly explored for the first time. Results revealed that after being separated, inactivated or immobilized, Hb can still induce the formation of chiral PANI successfully, suggesting that Hb can be used as the chiral inducers regardless of harsh reaction conditions. By examining the properties of PANI induced by modified Hb, it was found that Hb(inactivated)-PANI possessed excellent chirality, stability, and crystalline structure. The globin separated from Hb was demonstrated to have the ability of inducing the production of chiral PANI whereas the hematin from Hb had no capacity to direct enantio specificity for the PANI chains. Results indicated that Hb(immobilized)-PANI exhibited poor yield, doping state, and crystalline structure, indicating that the immobilization of Hb by entrapment was not bene cial to the polymerization reaction. Results also showed that the structure of Hb may have significant effects on the morphologies of chiral PANI.