Tungsten carbide with special spherical hollow microstructure was synthesized and tested as an electrocatalyst or electrocatalysts support for platinum. Both bulk WC and as-synthesized WC supported Pt were evaluated as hydrogen evolution catalysts. It was found that the synthesis temperature is crucial to the compositions and surface states of products, and has direct influence on HER activity. The WC possesses spherical micromorphology with a high specific surface area, and its hollow and cracked structural features are considered to be beneficial for its electrocatalytic ability and potential as electrocatalysts support. The bulk WC hollow microspheres displayed excellent HER activity. The 20% Pt/WC also exhibited better electrocatalytic performance than the commercial 20% Pt/C: the current density has obviously increased, and the kinetic parameters such as Tafel slope and exchange current density have obvious improvement as well. The investigations indicated that the as-synthesized WC could be considered as a potential electrocatalyst and electrocatalyst support. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.