We observed the photochemical hole burning in Sm 2 + -doped silicate glass samples at room temperature. Sm 2 + -doped Al 2 O 3 -SiO 2 glass samples and Na 2 O-Al 2 O 3 -SiO 2 glass samples were produced with the sol-gel method and a conventional melting and quenching method. The spectral hole for the Sm 2 + -doped Na 2 O-Al 2 O 3 -SiO 2 glass was shallow and poorly resolved compared to the hole in aluminosilicate glass. The difference is due to the 5 D 0 (zero phonon line) overlapping with the 4f 5 5d state. The hole width for a non-alkali aluminosilicate glass sample produced by the sol-gel method was somewhat larger than that of a sodium aluminosilicate glass sample. The hole width broadening in the gel-derived glass, is assumed to be due to its more open structure. We also examined the phase separation effect on photochemical hole burning in Sm 2 + -doped borosilicate glasses. Phase separation in our samples scarcely affected the photochemical hole burning and local structure around the rare earth-ion.