Two new boron imidazolate frameworks (BIFs), Zn₂[HBH(2-mim)₃]₂(1,2-PEA)₂(EG)₂ (BIF-120, EG = ethylene glycol) and Zn[BH(2-mim)₃](1,2-HPEA) (BIF-121), were successfully synthesized by mixing the KBH(2-mim)₃ ligand and the semirigid aromatic dicarboxylate ligand 1,2-benzenediacetic acid (1,2-H₂PEA) under solvothermal conditions. In this paper, the two samples were structurally characterized by single-crystal X-ray diffraction and tested by infrared spectroscopy (IR), UV-visible spectroscopy (UV-Vis), thermogravimetric analysis TGA and X-ray powder diffractions. In addition, the solid-state luminescent properties of these crystals were also investigated.