A liquid–liquid extraction system suitable for studies of chemical properties of Hs (element 108), in the form of HsO4, was developed using γ-emitting isotopes of its homologue Os. The system is targeted for the fast on-line extraction system SISAK, which operates in a continuous manner and is suitable for liquid-phase studies of transactinide elements. The distribution of OsO4 between various dilute NaOH solutions and toluene was studied. Both batch and SISAK on-line experiments were performed to develop an appropriate system. From analysis of the extraction curves equilibrium constants for the formation of the presumed complexes, Na[OsO4(OH)] and Na2[OsO4(OH)2], were obtained: K1=(1±0.5)×104 and K2=12±8, respectively. The SISAK system includes a liquid-scintillation detection system for α measurements. Due to quenching effects it is not possible to perform direct measurement of the aqueous phase α´s. Therefore, a two-stage extraction method that provides an indirect measurement of the activity in the aqueous phase was developed as part of the proposed system for Hs: Acidification of the raffinate from the first stage result in recovery of OsO4, which is highly extractable into toluene. The yield of extraction in the second step, from 0.01 M NaOH solution after acidification with H2SO4 solution, was (90±3) %.