Three phosphomolybdate hybrid derivatives, (H2bib)2.5{HP2Mo18O62}·2H2O (1), (H2bib){Sr⊂H4P6Mo18O73}·6H2O (2), (H2bib)3{Co(H2O)2}{Sr⊂P6Mo16ⅥMo2Ⅴ O73}·6H2O (3) (bib ​= ​1,4-Bis(imidazolyl)butane) were built by bib inducer via in situ hydrothermal reaction and fully characterized. Compounds 1 and 2 are bib modified Dawson and basket-like hybrids with complex topologies, respectively. In structure of 3, {P6Mo18O73} polyanions arranged in ABAB manner are alternately bridged by {Co(H2O)2} unit to yield an extended wavy chain, which was expanded into supramolecular sheets and infinite 3-D meshwork. The irregularly shaped tunnels are produced in the spatial structure of 3. The electrochemical tests show compound 3 presents enhance specific capacitance (797.8 ​F·g−1at 3 A/g), cycle efficiency (96.5% after the 5000th cycle), electrical conductivity, and catalytic activity than those of compounds 1 and 2 due to its structure advantages. Moreover, 3-GCE exhibits electrochemical responses to AA at potential of 0.3 ​V with the lower detection line of 0.16 ​μM, the wider linear range of 4.00 μM–4.72 ​mM, merit selectivity and reproducibility. The merit capacitive and sensing properties of 3 are attributed to introduction of transition metal Co, which not only provides additional redox active sites, but also bridges the basket clusters to form ordered tunnels that providing the necessary paths for ion or electron transmission. Three hybrid derivatives based on {P2Mo18}/{P6Mo18} were obtained induced by bib ligand via in situ hydrothermal reaction. Comparing compounds 1 and 2, 3 shows improved specific capacitance, electrochemical conductivity, and sensing performance for the detection of AA due to its structural advantages. Display omitted •Three hybrids based on {P2Mo18}/{P6Mo18} were obtained induced by bib ligand.•3 is an unique 3-D meshwork based on ABAB arranged {P6Mo18} and {Co(H2O)2} linker.•The irregularly shaped tunnels are produced in the spatial structure of 3.•3 shows excellent pseudocapacitance properties and improved electrical conductivity.•3 has electrocatalytic activity and good electrochemical sensing detection for AA.