In this paper, we report the design of a new functionalized tripodal ligand triCB-NTB (4,4′,4′′-(2,2′,2′′-nitrilotris(methylene)tris(1H-benzo[d]imidazole-2,1-diyl)tris(methylene))tribenzoic acid) and its assembly of Eu(III) homometallic or Zn(II)-Eu(III) heterometallic lanthanide-based metal–organic frameworks (MOFs). C₃ symmetric Eu(III) center is achieved in the homometallic MOF, [Eu(triCB-NTB)]·DMAc·4H₂O (1). The C₃ axis of the three coordinated imino N atoms on the propeller-extended central triCB-NTB ligand coincides with the C₃ axis that directs the three para-methyl carboxylic benzene arms on three surrounding ligands coordinating with the central Eu(III) simultaneously. Therefore, a (6, 3) pattern is formed in the framework with relatively large porosity. In the Zn-Eu heterometallic framework, [EuZn(triCB-NTB)(H₂O)(Cl)₂]·2DMAc·H₂O (2), the N atoms on the triCB-NTB are coordinated with Zn(II) and the carboxylic O atoms are coordinated with Eu(III). A paddle-wheel linked Eu(III)₂ cluster is formed and 1D loop-and-chain structure is obtained. Two ligands, two Zn(II) ions and two Eu(III)₂ clusters constitute one box-like unit on the loop chain. Due to the non-inversion symmetry imposed on the central Eu(III) and the large polarizability of the ligand, both one photon (OP) luminescence based on the energy transfer from the ligand to Eu³⁺ and two photon (TP) luminescence based on the hypersensitive transition of the Eu³⁺ ions are observed in the two lanthanide-based MOFs. This satisfies the urgent needs of multi-mode luminescent lanthanide complex. Simultaneously, N₂ gas and selective vapor adsorptions were also detected in the porous structure of complexes 1 and 2 due to their benzene-filled channels. The six-pointed-star like cavities in 1 can let the gas and vapor molecules go in and out smoothly subject to changes in the pressure, while the narrower and more irregular channels in 2 show irreversible adsorption behavior for benzene and cyclohexane vapor molecules in vacuum under room temperature.