Phase-pure beta-NiMoO4 yolk-shell spheres for lithium-ion battery anodes were prepared for the first time by one-pot spray pyrolysis, and their electrochemical properties were investigated. The yolk-shell-structured beta-NiMoO4 powders exhibited high initial discharge/charge capacities (1634/1253 mAh g(-1)) at a current density of 1000 mAg(-1). After 200 cycles, these powders exhibited a high discharge capacity of 1292 mAhg(-1), whereas the initial discharge capacity (1341 mAhg(-1)) of the filled structured NiMoO4 powders was dramatically decreased to 479 mA hg(-1). The significant enhancement of the cycling performance of the beta-NiMoO4 powders with ultrafine crystallite size was attributed to the structural stability of the yolk-shell structure. (C) 2015 Elsevier Ltd. All rights reserved.