Glass structures of obsidian and pumice samples were measured using electron diffraction. Amorphous, partly ordered, and nanocrystalline regions were distinguished and analysed separately. The deconvoluted atomic distances obtained from experimental diffraction patterns through total pair-distribution functions are consistent with distances for ideal SiO4 tetrahedra. Partly ordered structures in pumices are composed of plate-like fragments of tridymite/cristobalite layers, whereas obsidian contains quartz nanocrystals with abundant moganite-like planar faults. The validity of the structure-model of Goodman for silica glasses is discussed and an alternative interpretation is proposed for silicic volcanic glasses.