Two series of isoreticular chiral metal-organic frameworks assembled from Ln(III) (Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb), Na(I), and chiral flexible-achiral rigid dicarboxylate ligands, formulated as [NaLn(Tart)(BDC)(H(2)O)(2)] (S1) and [NaLn(Tart)(biBDC)(H(2)O)(2)] (S2) (H(2)Tart = tartaric acid; H(2)BDC = terephthalic acid; H(2)biBDC = biphenyl-4,4'-dicarboxylic acid), were obtained as single phases under hydrothermal conditions. The compounds have been studied by single-crystal and powder X-ray diffraction, thermal analyses (TG-MS and DSC), vibrational spectroscopy (FTIR), scanning electron microscopy (SEM-EDX), elemental analysis, and X-ray thermodiffractometry. The catalytic activity has been also investigated. The photoluminescence properties of selected compounds have been investigated, exhibiting room temperature tunable UV-vis-IR light emission.