Hydrothermal reactions of lanthanide metal salts with MeN(CH2CO2H)(CH2PO3H2) (H3L) and 5-sulfoisophthalic acid monosodium salt (NaH2BTS) lead to four isomorphous lanthanide carboxylate-phosphonate-sulfonate hybrids, namely, Ln(H2L)(HBTS)(H2O)(2).H2O (Ln = La (1), Pr (2), Nd (3), Gd (4)). Their structures have been established by X-ray single-crystal diffraction. The interconnection of the lanthanide(III) ions by carboxylate-phosphonate ligands results in a 1D double chain; these double chains are further bridged by bidentate bridging carboxylate-sulfonate ligands to form a <011> layer. The luminescent properties of compounds 3 and 4 have also been studied.