The invention discloses a method for preparing an enzyme electrode with an MWCNTs-TiO2/Nafion composite medium. In the method, MWCNTs-TiO2 core-shell nanocomposite materials are scattered into Nafion to prepare an organic-inorganic composite membrane as a fixed matrix for biological molecules for structuring a hemoglobin electrode, and a hemoglobin biosensor with fast response, high sensitivity and strong catalytic capacity is prepared by using the properties of large specific surface area, high surface reactivity, strong adsorption capacity, large electrical conductivity and the like of the MWCNTs-TiO2 core-shell nanocomposite materials and the properties of membrane forming, high chemical stability, high anti-interference capacity and the like of the Nafion. The biosensor has good biocompatibility, stability and repeatability, and has potential application in structuring biosensors. The sensor can be used for detecting the substances of hydrogen peroxide, trichloroacetic acid and the like, and has the advantages of low sensitivity, low detection limit and the like.