We have reported, for the first time, in situ growth of high-index {hk0} faceted concave Pt nanocubes on multi-walled carbon nanotubes (CNTs) via an electrochemical method in choline chloride-urea (ChCl-U) based deep eutectic solvents (DESs). Mechanistic studies indicate that a urea hydrogen bond donor (HBD) plays a key role in the formation of concave Pt nanocubes, in which the urea HBD preferentially adsorbs onto the {100} faces and blocks the growth of nanocrystals along the 〈100〉 axis. The as-prepared concave Pt nanocubes are characterized to be enclosed mainly with high-index {710}, {610} and {510} facets. It has been determined that the concave cubic Pt/CNT exhibits higher catalytic activity and stability than the flower-like Pt/CNT and commercial Pt/C catalysts, and this is ascribed to its high density of surface atomic steps and the synergistic effect between the CNT and Pt nanocubes.