Density, pH, viscosity, conductivity and the Raman spectra of aqueous NaB(OH)4 solutions precisely measured as functions of concentration at different temperatures (293.15, 298.15, 303.15, 313.15 and 323.15 K) are presented. Polyborate distributions in aqueous NaB(OH)4 solution were calculated, covering all the concentration range, B(OH)4? is the most dominant species, other polyborate anions are less than 5.0%. The volumetric and the transport properties were discussed in detail, both of these properties indicate that B(OH)4? behaves as a structure-disordered anion.