A new bismuth(III) complex [(1,10-phen)Bi(C ₂O ₄) _1.5], 1,10-phen = 1,10-phenanthroline, was synthesized with oxalate and phen ligands without by-products. The title complex was characterized by single crystal X-ray diffraction, FT-infrared Spectrum, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). 2D bismuth - oxalate - bridged layers are formed by oxalate ligands. Phen ligands are embedded in it which further stabilize the structure. The luminescence properties show that [(1,10-phen)Bi(C ₂O ₄) _1.5] can emit blue-green fluorescence, and π - π stacking and ligand-to-metal-charge transfer (LMCT) are predominant in it, which may have potential applications in the fields of crystal luminescent materials.