Abstract. The investigation results of clathrate properties GaSe〈β-cyclodextrin〈FeSO 4 〉〉 of the hierarchical architecture with the fourfold expansion at different degrees of a guest cavitations loading have been presented. Based on the frequency dependence of the specific complex impedance, the changes of the impurity energy spectrum expanded matrix parameters as a result of forming the supramolecular ensembles on its basis are clarified. For some architecture, impedance, photo and magneto responses showed the extraordinary behavior of the magnetoimpedance and photoconductivity and also the giant negative photodielectric and the colossal magnetocapacitance effects at room temperature, which open new possibilities of their practical application.