We studied the optical properties of sol-gel synthesized porous silica excited by synchrotron radiation in the 4-10 eV range. The spectral and temporal characteristics of the ultraviolet photoluminescence at about 3.7 eV are reported. The UV emission results from the contribution of two different centers: the first one centered at 3.7 eV with a decay time of 2.0 ns and the second one peaked at 3.9 eV with a decay time of 20 ns. We propose to assign the observed luminescence to different interacting surface silanols.