Eight new lanthanide derivatives containing 6-peroxoniobio-4-phosphate building block, [LnIII(H2O)6]2[H4(NbO2)6P4O24]·nH2O [Ln = Eu (1), Gd (2), Tb (3), Dy (4), Ho (5), Er (6), Tm (7), Yb (8), 1–5, 7, 8 n = 12; 6 n = 9], have been successfully obtained using an in-situ strategy and fully characterized in the solid state by single-crystal X-ray diffraction, IR spectra, TG-MS, PXRD. Structural analyses indicate that these isostructural polyanions 1–8 consist of one [P4(NbO2)6O24]10− (P
4
(NbO
2
)
6) clusters and two pendant Ln3+ cations. In these compounds, P
4(NbO
2
)
6 clusters are connected by lanthanide cations to form extended two-dimensional architectures. The approach takes advantage of the ability of in-situ formed P
4(NbO
2
)
6 cluster to build frameworks by using it as ligands to lanthanide ions. The photoluminescence (PL) and lifetime decay behaviors of 1, 3 and 4 in solid state have been performed at room temperature. The PL emission of 1, 3 and 4 is mainly derived from the characteristic 5D0→7FJ (J = 1, 2, 3, 4), 5D4→7FJ (J = 6, 5, 4, 3) and 4F9/2→6H J (J = 15/2, 13/2, 11/2) transitions of the EuIII, TbIII and DyIII cations, respectively.