The existing technological schemes for processing rhenium-containing raw materials involve the recovery of Re from solutions, which can be effectively achieved by anion exchange method. The application of anion exchange also allows to study rhenium state in aqueous solutions and to develop analytical control methods. The present work is focused on investigation of ion exchange equilibrium in the analytical system Re(VII)-HCl-$SnCl_2$-KSCN-anion exchanger by means of sorption-desorption method as well as by electron, IR- and diffuse reflection spectroscopy. It was shown that rhenium can be quantitatively recovered from this system. It is proposed to use the sorption-spectroscopic method for Re(VII) determination in aqueous solutions. The calibration curve is linear in the concentration range of 0.5-20.0 mg/L (sample volume is 25.0 mL) and the detection limit is 0.05 mg/L. The presence of Mo(VI), Cu(II), Fe(II, III), Ni(II), Zn(II) as well as $K^+,;Na^+$ do not hinder the solid-phase determination of rhenium. Rhenium (VII) determination by diffuse reflection spectroscopy was carried out in model solutions as well as in samples of river-derived water and in solutions obtained after the dissolution of spent catalysts.