Two new flexible exo-bidentate ligands were designed and synthesized, incorporating different backbone chain lengths bearing two salicylamide arms, namely 2,2′-(2,2′-oxybis(ethane-2,1-diyl)bis(oxy))bis(N-benzylbenzamide) (L^I) and 2,2′-(2,2′-(ethane-1,2-diylbis(oxy))bis(ethane-2,1-diyl))bis(oxy)bis(N-benzylbenzamide) (L^II). These two structurally related ligands are used as building blocks for constructing diverse lanthanide polymers with luminescent properties. Among two series of lanthanide nitrate complexes which have been characterized by elemental analysis, TGA analysis, X-ray powder diffraction, and IR spectroscopy, ten new coordination polymers have been determined using X-ray diffraction analysis. All the coordination polymers exhibit the same metal-to-ligand molar ratio of 2 : 3. L^I, as a bridging ligand, reacts with lanthanide nitrates forming two different types of 2D coordination complexes: herringbone framework {[Ln₂(NO₃)₆(L^I)₃·mC₄H₈O₂]_∞ (Ln = La (1), and Pr (2), m = 1, 2)} as type I,; and honeycomb framework {[Ln₂(NO₃)₆(L^I)₃·nCH₃OH]_∞ (Ln = Nd (3), Eu (4), Tb (5), and Er (6), n = 0 or 3)} as type II, which change according to the decrease in radius of the lanthanide. For L^II, two distinct structure types of 1D ladder-like coordination complexes were formed with decreasing lanthanide radii: [Ln₂(NO₃)₆(L^II)₃·2C₄H₈O₂]_∞ (Ln = La (7), Pr (8), Nd (9)) as type III, [Ln₂(NO₃)₆(L^I)₃·mC₄H₈O₂·nCH₃OH]_∞ (Ln = Eu (10), Tb (11), and Er (12), m, n = 2 or 0) as type IV. The progressive structural variation from the 2D supramolecular framework to 1D ladder-like frameworks is attributed to the varying chain length of the backbone group in the flexible ligands. The photophysical properties of trivalent Sm, Eu, Tb, and Dy complexes at room temperature were also investigated in detail.