A ligand 5,5′-methylene-bis(8-hydroxyquinoline)(Hqq)was synthesized by condensation reaction at low temperature and was subsequently coordinated to gallium ions to prepare the polymer of tis(5,5′-methylene-bis(8-hydroxyquinoline)gallium (Gaqq3)n. Both chemical structure and phase structure of the ligand and complexes were characterized by Infrared absorption spectrum and X-ray diffraction (XRD). The thermal stability of the complexes was studied by thermogravimetry (TG). The photo-physical properties of the complexes were investigated by ultraviolet absorption spectrum (UV), fluorescence excitation spectrum and emission spectrum. The result indicated that (Gaqq3)n is a thermally stable material, whose decomposition temperature is 443.6 ℃. The ultraviolet absorption bands of (Gaqq3)n are in the range of 250-500 nm, with a relatively strong band tail absorption between 500 and 650 nm, which shows that the band-gap defect states exists in the forbidden band. The fluorescence excitation band of (Gaqq3)n is located at 380-456 nm, and (Gaqq3)n. emits orange-red fluorescence with the emission peak at 568 nm, which shows that the fluorescence emission of (Gaqq3)n is mainly attributed to the charge transfer transitions from phenol to ring pyridine ring, while the π→π* transition of benzene ring is deactivated by non-radiative transition, and makes no contribution to fluorescence emission. (Gaqq3)n optical band gap is 2.49 eV. Compared with the fluorescence emission peak of Gaq3, the fluorescence intensity of (Gaqq3)n decreases, which is attributed to the distortion of the two quinoline rings connected to the methylene, hence leads to the poor rigidity and coplanarity of (Gaqq3)n, thus affects fluorescence emission intensity. Because of the extending of the molecular conjugation system, π electron of (Gaqq3)n is more delocalized, resulting in the redshift of fluorescence emission peak. (Gaqq3)n is expected to be applied in organic light emitting display and organic photovoltaic devices.