Polyoxometalates (POMs) based metal-organic frameworks (POMOFs) integrate the merits of POMs with excellent redox properties and MOFs with highly ordered porous crystalline structures, which show potential electrochemical applications relying on the synergistic catalytic effect. Here, two new Keggin-type POMOFs [Cd(btbu)2(H2O)2(PMo12O40)] (CUST-636), [Cd(btbu)2(H2O)(SiW12O40)0.5](CUST-638) are synthesized using flexible ligand of 1,4-bis(1,2,4-triazol-1-yl)butane (abbreviated as btbu) as a ligand by hydrothermal method. PXRD, IR, and TG analysis were carried out on CUST-636 and CUST-638. Then, they were prepared into electrode materials (referred to as 636-GCE and 638-GCE), to explore the electrocatalytic properties. 636-GCE and 638-GCE show good electrocatalytic redox performance against KBrO3, KNO2, K2Cr2O7 and AA. Furthermore, detection of trace Cr(VI) was conducted using electrochemical sensors 636-GCE and 638-GCE. The low detection limits (LODs) of CUST-636 and CUST-638 were 0.32 and 0.45 μM, respectively, which were lower concentrations of Cr(VI) in drinking water than the maximum allowable concentration specified by the World Health Organization (WHO).