Nanocrystals of Rh, an important member of the noble metal catalyst family, have wide applications in heterogeneous catalytic reactions. Controlling the morphology of these noble metal nanocrystals has become an effective strategy for improving their catalytic activity and durability. In this work, well-defined Rh nanodendrites with very thin triangular branches as subunits are synthesized using a facile diethylene glycol reduction method, assisted by polyethyleneimine as a complex-forming agent and surfactant. For the first time, the methanol oxidation reaction (MOR) on Rh nanocrystals with a well-defined morphology is investigated using various electrochemical techniques in an alkaline medium. Unexpectedly, the as-prepared Rh nanodendrites, with ultrathin nanosheet subunits, exhibit superior electrocatalytic activity and durability during the MOR in an alkaline medium, indicating that Rh nanocrystals with specific morphology may be highly promising alternatives to Pt electrocatalysts in the MOR in an alkaline medium.