Rod-like α-MoO3 is successfully designed by alternating voltage induced electrochemical synthesis (AVIES) approach. The morphology and texture of MoO3 is effectively controlled by applying various calcination temperature of 300–600°C. Notably, the α-MoO3 microrods growing along [001] direction have the high aspect ratio, and the randomly stacked structure can facilitate the charge transfer and offer more active sites for sodium storage. When utilized for sodium-ion batteries, it presents the high charge capacities of 305mAhg−1 at 1C and 143mAhg−1 at 10C. Even after 3000 cycles at 10C, a significant capacity of 108mAhg−1 is still delivered, highlighting its marvelous electrochemical properties. This work may be a compelling exploration for developing metal/metal oxides materials for sodium storages by AVIES.