A novel Tb(III) coordination polymer and discrete complexes have been synthesized by one-pot reaction utilising flexible tripodal Schiff base ligands, tris[2-(salicylideneamino)ethyl]amine (H 3 L) derivatives. Condensation of 5-methylsalicylaldehyde (5-MeSal) with tris(2-aminoethyl)amine (tren) in the presence of Tb(CF 3 SO 3 ) 3 in a 3:2:1 (=5-MeSal:tren:Tb(III)) molar ratio gives Tb 1 L, and the deprotonated ligand encapsulates the Tb(III) in its N 4 O 3 cavity in endo-coordination. Here, the excess tren acts as a base to dissociate the proton of the ligand. Decreasing the amount of tren to a 3:1:1 ratio gives [Tb(H 3 1 L) 2 ](CF 3 SO 3 ) 3 ·H 2 O. In this compound, the Tb(III) centre is coordinated by two H 3 1 L ligands adopting the exo-capping mode to provide three O atoms outside the cavity of H 3 1 L. Replacing Tb(CF 3 SO 3 ) 3 with Tb(NO 3 ) 3 in the above reaction induced a substantial structural change to coordination polymer [Tb(H 3 1 L)(NO 3 ) 3 ·DMF·1/6H 2 O] n . In this polymer, the ligand adopts an unprecedented exo-bridging coordination mode, which is the first bridging mode observed for this tripodal Schiff base ligands. Three aromatic rings of the exo-bridging ligand are close to each other by CH⋯π interactions and each O atom coordinates to three different Tb(III) ions to construct a three-dimensional polymeric connection. The 3D framework has the nano-pore structure with inner walls that consisted of alternately appearing hydrophilic and hydrophobic regions. The present study shows that the tripodal Schiff base ligand can be a novel class of flexible building block to construct the Ln(III) coordination polymer.