Two coordination polymers (CPs), [Hg(Bpbp)X2]n (X = Br (1), I (2), Bpbp = 4,4′-bis(4-pyridyl)-biphenyl), were synthesized via solvothermal synthesis methods, and were further fully characterized by single crystal X-ray diffraction, powder X-ray diffraction, elemental analyses, FT-IR spectroscopy, and thermogravimetric analyses. The two CPs exhibit similar one-dimensional zigzag chain structures constructed by Bpbp ligand connecting Hg(II) cations with halide ions as terminal ligands, while the zigzag chains show different configurations, symmetries and packing modes. The results of photoluminescence experiments and DFT calculations indicate that both the halide anions and conjugated Bpbp ligands show important roles in the emission process of CPs, and halide anions may tune the luminescence properties of CPs.