Infrared photon dissociation (IRPD) spectra of the NaSO4 (H2O)(n) clusters with up to five water molecules have been studied using quantum chemical calculations. Our calculation reveals that the splitting of the peaks in the similar to 8001300 cm(1) region of the IRPD spectra, which contains the information on SO bond stretching of the anion, indicates the deviation of the cation from the C-3v axis as well as the asymmetric distribution of the water molecules. The frequency of the H-bonded OH stretching peak in the similar to 23003000 cm(1) window, on the other hand, provides information on the position of the newly added water molecule with respect to the cation. The IRPD technique thus provides abundant structural information on the early stage of the microsolvation and has the potential to become a powerful tool complementary to photoelectron spectroscopy.