The microstructure design based on the development of heterostructure provides a new way for high strength and ductility Mg alloys. However, the wear property, as an important service performance, of Mg alloys with heterostructure is scarcely investigated. In this work, a high strength and ductility AZ91 Mg alloy with multiheterostructure was prepared via a processing route combined industrial-scale equal channel angular pressing (ECAP) and aging. The multiheterostructure consists of the heterogeneous grain structure and heterogeneous precipitates. The dry sliding wear behavior of this multiheterostructured (MH) alloy is investigated compared to the as-cast alloy. The impacts of the applied load and duration time on the wear volume and coefficient of friction (COF) are analyzed, and the wear mechanism is further discussed. The result indicates that although the MH alloy exhibits high-desirable strength-ductility synergy, it shows a poorer wear resistance but a relatively lower COF compared to the as-cast alloy at the present condition. The wear mechanism of both alloys mainly involves abrasive wear, as well as mild adhesion, delamination, and oxidation. In comparison, the MH alloy shows relatively severe adhesion, delamination, and oxidation. The poor wear resistance of the MH alloy at the present dry sliding wear condition is linked to the abundant grain boundaries and fine precipitates. Therefore, one should reasonably use the MH Mg alloy considering the service conditions to seek advantages and avoid disadvantages.