Among the investigated organic extractants, both for preparation of bovine and human cord-derived polyHb-SOD-CAT-CA complex, n-hexane indicated to have much less negative influence on the properties and stability of Hb and enzyme molecules, including SOD, CAT, and CA. Moreover, the obtained human cord blood polyHb-SOD-CAT-CA also showed effective oxygen-carrying properties and enzyme activities, suggesting the promising application prospects of polyHb-SOD-CAT-CA and the new generation HBOC products in the future.