Two new dodeca-niobate materials, K3[Nb2O2][H7SiNb12O40]·16H2O (1) and [Cu(en)2]9[(VNb12V1.69Nb0.31O42en0.31)2]·20.69H2O (2) (en = ethylenediamine), have been obtained under hydrothermal conditions and characterized by IR, UV-Vis, XRD, and single crystal X-ray diffraction analysis. Single crystal X-ray analysis reveals that compound 1 presents a reasonable bridging layer structure model and that K plays a great role in the three-dimensional structure. Compound 2 is the first capped Keggin POM with organic ligand chelating the capping atom. The photocatalytic hydrogen evolution and styrene epoxidation catalytic properties of the two compounds were also assessed. Additionally, compound 1 is also a good photocatalyst to degrade RhB.