In this contribution, a novel sulfate-ion-controlled synthesis is developed to fabricate freestanding nickel hydroxide nanoarrays on Ni substrate. As an inorganic morphology-controlled agent, SO ions play a critical role in controlling the crystal growth and the nanoarray morphologies, by modulating the growth rate of adsorbed crystal facets or inserting into the metal hydroxide interlayers. By controlling the SO concentration, the nanostructured arrays are tailored from one-dimensional (1D) Ni(SO ) (OH) nanobelt arrays to hierarchical β-Ni(OH) nanosheet arrays. With further graphene oxide modification and postheat treatment, the obtained NiO/graphene hybrid nanoarrays show great potential for high-performance sodium-ion batteries, which exhibit a cyclability of 380 mAh g after undergoing 100 cycles at 0.5 C and reach a rate capability of 335 mA h g at 10 C.