Three inorganic–organic hybrids based on Keggin tungstophosphates and lanthanides, [Pr(NMP) 6 (PW 12 O 40 )] n (1), [Eu(NMP) 6 (PW 12 O 40 )] n (2), and [Er 2 (NMP) 12 (PW 12 O 40 )][PW 12 O 40 ] (3) (NMP=N-methyl-2-pyrrolidone), have been synthesized and characterized by elemental analysis, IR, UV–vis, and single-crystal X-ray diffraction. Compounds 1 and 2 exhibit 1D infinite zigzag chain structures, while compound 3 exhibits an ionic asymmetric structure due to lanthanide contraction. The three compounds are all photochromic. The magnetic susceptibility for 1 measured over the range 2–300K shows that there is the dominant antiferromagnetic interaction in the compound. The results of luminescent properties show that compound 2 displays an interesting selectivity for Zn 2+ ions.