The electrochemical studies of Sb (III) have been carried out in room temperature ionic liquid 1-butyl-1-methylpyrrolidinium dicyanamide (BMP-DCA). Cyclic voltammetry results indicated that the reduction of Sb (III) on GC electrode needs larger overpotential than on Pt electrode. Analysis of the chronoamperometric transient behavior revealed a three-dimensional instantaneous nucleation/growth process for the electrodeposition of Sb on GC electrode. The nuclei density increased and the nuclei radius decreased as the overpotential increased. The calculated diffusion coefficient of Sb (III) specie was 1.23× 10− 7 cm 2 s− 1. For comparison, a weaker ligand property ionic liquid BMP-TFSI was used for electrodeposition. The morphology and the crystallinity of the electrodeposits from the different ionic liquids are investigated by SEM, and XRD. Granular shape of Sb was obtained from BMP-DCA even at more negative potential, but dendrite structure was obtained at more negative potential. A granular shape was been evidenced at more positive potential in BMP-TFSI. The XRD patterns revealed the Sb obtained from BMP-DCA is amorphous, but rhombohedral Sb was obtained from BMP-TFSI. This study reveals the anions of the ionic liquids have a significant influence on morphology and crystallinity during the electrodeposition process.