An open framework gallium selenide, Ga4Se7(en)(2).(enH)(2), has been prepared by the direct reaction of gallium (Ga) and selenium (Se) in ethylenediamine (en), in which both-covalent and hydrogen bonds have been employed to combine the inorganic structures and organic spacers to build layers with micropores. Its structure has been determined by X-ray diffraction. Its thermal and optical properties have been characterized by TGA and UV-vis, Raman, and IR spectroscopies, respectively.