Two novel entangled POM-based coordination polymers (CPs), namely [Co-2(L)(5)(H2O)(2)(SiW12O40)] (1) and [Cu-2(L)(3)(H2O)(2)(SiW12O40)]center dot H2O (2) (L = 4,4'-bis((1H-1,2,4-triazol-1-yl)methyl) biphenyl), have been hydrothermally synthesized. Compound 1 presents an unprecedented 2D + 2D -> 3D polypseudorotaxane motif. The fascinating self-catenated framework of compound 2 contains three types of helical chains. In addition, the photocatalytic properties of compounds 1 and 2 have also been investigated.