X-ray photoelectron spectroscopy has been used to examine the chemical states of fluorine in the glasses of composition xCaF2(50 – x)CaO · 50SiO2 (x = 5, 10, 15, 20, and 25 mol %) and xCaF2(50 – x/2)CaO(50 – x/2)SiO2 (x = 5, 10, 15, and 20 mol %). The analysis of the F1s spectra indicated that Ca2+ and F- ions introduced as CaF2 are favorably located among the Si–O skeleton forming Ca–F clusters. The fraction of the bridging and nonbridging oxygen atoms was derived from the O1s spectra, and the network of the fluorine-containing glasses was concluded to depend only on the ratio CaO/SiO2.