The use of a conjugate N-containing ligand resulted in the decreasing of structural dimensions from 2D network of [Tb(2-pyia)(Ac)(H2O)] (CP1) to 1D chain [Tb(2-pyia)(Ac)(IDP)] (CP2) (2-H2pyia = 5-(pyridin-2-ylmethoxy) isophthalic acid and IDP=imidazo[4,5-f]-[1,10] phenanthroline). Both of them exhibit the characteristic luminescence of Tb ions and could have high fluorescence sensing properties for cefixime and fluridine. The different sensing properties for nitro explosives are manifested as CP1 for nitrobenzene and CP2 for 4-nitrophenol due to the difference in structure. Furthermore, CP2 exhibits the ratiometric fluorescence sensing for Fe3+ ion with a low detection limit of 0.405 μM. The fluorescence sensing mechanism of the two Tb complexes for different analytes was investigated using experimental methods and theoretical calculations. CP1 was used for the detection of Flu residues in the actual system and better results were obtained. The work shows the introduction of the chelated ligand might affect the structural and sensing performance changes of coordination polymers.