The structural variations of silica gels heated at different temperatures have been firstly studied using Nd(3+) as a probe by photoacoustic spectroscopy (PAS), together with IR spectroscopy and thermal analysis. With increasing temperature, the f-f transitions of Nd(3+) show a red shift and the PA intensities increase. The PA branching vector of the transitions from ground state to 4G(5/2)+(2)G(7/2), which are hypersensitive transitions, increase and the others decrease or change little. These indicate that the covalency of the bond that Nd(3+) forms increases and the symmetry around Nd(3+) decreases, which reflects the structural variations of silica gels.