The design and fabrication of non-Pt catalysts with excellent electrocatalytic performance toward methanol oxidation play a crucial role in the commercialization of direct methanol fuel cells (DMFCs). Herein, we propose a facile and robust strategy for the preparation of ultrafine Rh nanocrystals grown onto a boron and nitrogen codoped carbon support with a horn-shaped structure as Pt-alternative anode catalysts for DMFCs. The as-obtained hybrid nanoarchitecture possesses interesting structural features, including large specific surface area, numerous internal open pores, abundant B and N species, and homogeneous Rh dispersion. Benefiting from these superior properties, the resulting catalyst exhibits exceptional methanol oxidation performance with a large electrochemically active surface area of 182.4 m2 g-1, a high mass activity of 2350.5 mA mg-1, and good long-term durability, significantly outperforming Rh catalysts supported by conventional carbon supports and widely used Pt/carbon black and Pd/carbon black catalysts.