monofunctional catalysts, multifunctional catalysts have distinct advantages over them, such as cost reduction and simplified systems. [6] Thus, developing multifunctional catalysts is essential to achieve high energy conversion efficiency of these devices.High entropy alloys (HEAs), as a type of emerging catalysts, are generally defined as alloys that contain five or more metallic elements and each principal element ranges from 5 to 35 at%. [7] A large number of multiple active sites of HEAs can break the existing limitations, providing new insights for rational design of high-performance alloy catalysts. [8] Moreover, the binding energy of reactants on HEAs [9] can be modulated almost in a continuous form by super-rich elemental combination and ratio. [10] The varied coordination environments may also provide active sites for various types of catalytic reactions, implying that HEAs are suitable for multifunctional catalysis. [11] At present, the state-of-art electrocatalyst is platinum (Pt) for ORR and HER, [1,12] and IrO 2 and RuO 2 for OER. [4,13] Preparing HEAs with cheap transition metals [8,14] can not only reduce the usage of platinum group metal but also modulate the electronic structure and improve the catalytic performance of these alloy catalysts. [15] Furthermore, specific surface facets, strain, [16] and coordination environment of surface atoms [17] remarkably affect the catalytic activity of nanosized metal catalysts, which can be well regulated by selective combination of multi-metal elements in HEAs. High-index facets are usually more active for breaking and forming chemical bonds and exhibit higher catalytic activities than low-index facets due to the lower coordinated surface atoms of the high-index facets. [18] Exposure of high-index facets can be achieved by shape-controlled synthesis of polyhedron nanocrystals. However, the low-index planes usually take over the high-index ones on account of their higher growth rates than the high-index ones, it is thus very challenging to prepare metal nanocatalysts encompassed with high-index facets. [19] Currently, most reported HEAs are usually spherical nanoparticles enveloped by low-index facets. [20] The preparation of nanocrystals with high-index facets and exploration of the correlation of catalytic performance with shape and structure of nanosized HEAs remain unexplored. It is essential to develop High entropy alloy (HEA) catalysts exhibit excellent multifunctional catalytic performance due to the synergistic effect of multi-metal components. However, shape-controlled synthesis of such kinds of HEA catalysts, especially those with high index facets, still faces great challenges, limiting further enhancement of their catalytic performance. Herein, one-pot synthesis of convex cube-shaped Pt 34 Fe 5 Ni 20 Cu 31 Mo 9 Ru HEA catalysts which possess rich (310) facets and a diagonal crystalline size of 38.5 nm is reported. Transmission electron microscopy measurements indicate cube-shaped nanocrystals are obtained first and further selective growth of ...