The chemical species of silica in NaCl solutions of different concentrations were identified by FAB-MS (fast atom bombardment mass spectrometry). The basic structures of silica species, such as cyclic pentamer (Si5 (OH)9O6-), linear pentamer (Sis(OH)11O5-), cyclic hexamer (Si6(OH)9O8-, Si6(OH)11O7-) and linear hexamer (Si6(OH)14 O6-), were identified, in addition to dimer (Si2(OH)5O2-), trimer (Si3(OH)7O3-) and cyclic tetramer (Si4(OH)7O5-). The patterns of changes of the peak intensities of the silicate complexes relative to the dimer with increasing NaCl concentration were classified into two types: that represented by linear silicate complexes and the other by cyclic silicate complexes. The differences in the type of chemical species and their changes according to the NaCl concentration reflect the number of bonds necessary for polymerization and hydrolysis of the silica complexes. The differences between the linear and the cyclic silicate type have some implications on the dissolution mechanism of silicate complexes, the hydration of the molecules and the equilibrium between solubility, hydrolysis, polymerization and the salting-out effect in NaCl solution.