ZnSe-GaAs(001) heterovalent quantum structures, multiple quantum wells (MQWs), were fabricated. Since the band offsets in this heterovalent heterostructure are controllable, different offsets can artificially be put at both sides of the GaAs wells, which may lead to modification of the electronic properties of the MQWs. This hypothesis was examined by the optical absorption measurement. Consequently, by changing the valence band offset at the GaAs-on-ZnSe interface from 0.6 to 1.1 eV, while keeping that at ZnSe-on- GaAs constant at 0.6 eV, the absorption edge energies of the MQWs shifted from 1.43 to 1.37 eV. This indicates the presence of an internal electric field and the capability of controlling the electronic properties of heterovalent MQWs with the completely same structural parameters. The numerical analyses of the Poisson and Schrddinger equations well explain the trend of this experimental result.