The adsorption of Sb on the high index Si (5 5 12) has been studied at higher substrate temperature (HT) (800°C), using in situ surface characterization techniques like Auger Electron Spectroscopy (AES), Low Energy Electron Diffraction (LEED), and Electron Energy Loss Spectroscopy (EELS). The surface morphology of this high index Si (5 5 12) surface has row like trenches along (110) direction. We have performed the study of Sb adsorption and desorption on the Si (5 5 12) substrate held at different temperatures. The different pathways adopted during adsorption and desorption have suggested the dominant role of kinetics I forming various surface phases on the Si (5 5 12) substrate. The adsorption at room temperature resulted in the formation of (225) surface phase, while the adsorption at 680°C resulted in the (337) phase. The sequential thermal desorption of the room temperature and high temperature adsorbed surface resulted in the formation of (337) phases at 800°C, with anisotropic growth along one direction. While the adsorption at 800°C resulted in the formation of anisotropic (337) like phases, the further increase in the coverage formed a 2x Si (225) phase. Annealing this 2x Si (225) phase again resulted in the formation of anisotropic (337) phase. Thus formation of interface by controlling the growth kinetics can result in the formation of various tailored structures with desired properties.