Laser photooxidation is used to form a surface antimony layer on p-type GaSb and GaAs0.06Sb0.94. The emerged Sb/III-Sb interface is studied by a combination of the Raman and photoluminescence spectroscopy supported by Kelvin probe microscopy and atomic force microscopy. The laser power density controls the thickness and structure of the Sb layer. Laser photooxidation thickens the amorphous Sb layer that emerged after native oxide formation. The thickening decreases the bandgap photoluminescence intensity and increases surface band bending. Further increase in the laser power density forms a multilayered antimonene phase with a rhombohedral structure. The crystalline Sb layer decreases the surface band bending due to changes in the work function. For the crystalline layer, the PL intensity further decreases. The effective work function model explains the experimental results. Finally, the study shows that it is possible to modify surface optoelectronic properties with a submicrometer lateral resolution.