A study on solvent extraction of sulfuric acid by tri-octylphosphine oxide (TOPO) in n-heptane has been made. Extraction coefficients of H2SO4 as a function of H2SO4 concentration in aqueous phase, and extractant concentrations in organic phase have been studied. The composition of extracted species, equilibrium constants of extraction reaction have been evaluated. These results are important for interpreting extraction equilibrium data of uranium(VI) or other metal ions with TOPO in sulfuric acid media.