The surface reactions of silica film($SiO_2-P_2O_5-B_2O_3-GeO_2$) with fluorocarbon plasma has been studied by using angle -resolved x-ray photoelectron spectroscopy(XPS). It has been confirmed that residual carbon consists of C-C and C-CFx bonds and fluorine mainly binds silicon in the case of etched silica by using $CF_4$ gas plasma. The surface reaction of silica with various fluorocarbon gases, such as $CF_4,C_2F_6 and CHF_3$ were investigated. XPS results showed that though the etching gases were changed, the elements and binding states of the residual layers on the etched silica by using various fluorocarbon gas plasma were nearly the same . This seems to be due to the high volatility of byproducts, that is, $SiF_4 and CO_2$ etc..