Phase-pure β-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 β-NiMoO4 powders exhibited high initial discharge/charge capacities (1634/1253mAhg−1) at a current density of 1000mAg−1. After 200 cycles, these powders exhibited a high discharge capacity of 1292mAhg−1, whereas the initial discharge capacity (1341mAhg−1) of the filled structured NiMoO4 powders was dramatically decreased to 479mAhg−1. The significant enhancement of the cycling performance of the β-NiMoO4 powders with ultrafine crystallite size was attributed to the structural stability of the yolk-shell structure.