The surface properties after plasma etching of TiW alloy using the chemistries of BCl$_{3}$ and SF$_{6}$ gases with varying mixing ratio have been investigated using XPS(X-ray photoelectron spectrocopy). The elements existed on the etched sampled have been extracted with BCL$_{3}$/SF$_{6}$ ratio and their chemical binding states have also been analysed. It was confirmed that the thickness of native oxide formed on the TiW films is thinner than 10nm by using Ar sputtering. At the same time, the roughness of etched surface has been esamnied using AFM (atomic force microscopy). on the basis of the basis of this results, the relations between the caanges of oxygen contents detected by XPS and the rouhness of etched surface have been discussed. And the etch rate and etched profile of Tiw films have been examined and the changes of the etch rate and etched prfile have been discussed with XPS results. From XPS results, the role of passivation layer consisted of Ti-S compound with XPS results. From XPS results, the role of passivation layer consisted of Ti-S compound has been proposed. Ti-S compound seems to make a role of passivation layer that surpresses Ti-O formation.ion.