In this paper we present a review of the main results we obtained studying the emission properties of mesoporous silica in the UV-VIS range. Two main emission bands were investigated, the blue one, peaked in the 400–450 nm range, and the UV one, centered at about 300–350 nm, both excited in the UV and vacuum UV range. The origin of the two bands, investigated through optical spectroscopy techniques, is discussed in terms of possible surface emitting centers probing the samples with different chemical and physical treatments or exploiting different morphological and textural properties of the samples obtained by properly engineering the sol-gel synthesis.