Deliberately controlling organic ligand transformation in situ has remained a challenge for the construction of polyoxometalate (POM)-based inorganic organic hybrids. In this work, four POM-based hybrids assembled from an in situ bifurcating organic ligand-[Cu-2(DIBA)(4)](H3PMo12O40)center dot 6H(2)O (1), [Cu-2(DIBA)(4)] (H4SiW12O40)center dot 6H(2)O (2), [Ag(HDIBA)(2)](H2PMo12O40)center dot 2H(2)O (3), [Ag-3(HDIBA)(2)(H2O)][(P2W18O62)(1/2)]center dot 4H(2)O (4) (DIBAH = 3,5-di(1H-imidazol-1-yl) benzoic acid)-have been designed and obtained under hydrothermal conditions. Compounds 1 and 2 are isostructural, displaying a three-dimensional (3D) 2-fold interpenetrating framework with two types of channels, and the bigger channels are occupied by Keggin polyoxoanions and crystallization water molecules, but only crystallization water molecules in the smaller ones. Compound 3 displays a 3D supramolecular structure constructed from {Ag(HDIBA)(2)} segments and PMo(12)O(40)3-polyoxoanions through hydrogen bonding interactions. Compound 4 shows a 3D 2-fold interpenetrating framework based on (3, 3, 4)-connected network, which is constructed from {Ag-3(HDIBA)(2)}(n) chains and P2W18O626- polyoxoanions as linkers. The DIBAH ligand was generated in situ from 3,S-di(1H-imidazol-1-yl)benzonitrile by deliberate design, which illustrates that the strategy to construct novel POM-based hybrids by controlling ligand transformation in situ is rational and feasible. In addition, the effects of the central metal and POMs on the structures of the target compounds were discussed. Finally, the electrochemical and photocatalytic properties of compounds 1-4 have been investigated in this paper.