 A facile scalable synthesis of hierarchical Sb/C micro-/nanohybrid has been addressed in this work, which possesses the advantages of both micrometer and nanometer scale structures as lithium-ion battery anode. Difunctional methacrylate monomers are used as solvent and carbon source as well. Liquid precursor of antimony(III) n-butoxide is dissolved in the resin monomer solution, and further incorporated into the cross-linking polymer network via photo polymerization. Through calcination in argon/hydrogen atmosphere, antimony nanoparticles are in situ formed by carbothermal reduction, and homogeneously embedded in the in situ formed micrometer sized carbon matrix. The morphology, structure, crystallinity, spatial dispersion, composition, and electrochemical performance of the Sb/C micro-/nanohybrid are systematically investigated. The cyclic and rate performance of the Sb/C micro-/nanohybrid anode have been effectively improved compared to the pure carbon anode. A reversible capacity of 362 mAh g−1 is achieved with a reasonable mass loading density after 300 cycles at 66 mA g−1, corresponding to capacity retention of 79%. With reducing mass loading density, the reversible capacity reaches 793 mAh g−1 after 100 cycles. Moreover, the electrochemical performance of Sb/C micro-/nanohybrid as sodium-ion battery anode is also investigated in this study.