In this work, PtFeCu concave octahedron nanocrystals were synthesized by a one-pot solvothermal method. The PtFeCu concave octahedron nanocrystals were applied as an electrocatalyst for the electrooxidation of methanol and have shown high electrocatalytic activity and long-term durability. The electrocatalysis performances of the PtFeCu concave octahedron nanocrystals are better than those of the PtFe and PtCu nanocrystals and commercial Pt/C. The synergistic effect of the Pt, Fe, and Cu metals and the unique concave octahedron morphology may be the main cause of the superior electrocatalytic performances of the PtFeCu nanocrystals. The PtFeCu concave octahedron nanocrystals have a potential application as an anode catalyst for direct methanol fuel cells.