Proton exchange membrane fuel cells (PEMFCs) are developing into very meaningful clean energy to fundamentally address environmental pollution. Among which the most studied Nafion series membranes are limited under large-scale use, and some strong oxidizing groups such as hydrogen peroxide will attack the structure of Nafion, shortening the lifespan of PEMFCs. Therefore, it is crucial to develop a proton-conductive material with strong stability and broad application. In this study, a novel hourglass-type P4Mo6-based POMOFs denoted as (H2timb)2[Mn3(H3P4Mo6O31)2]·4H2O was synthesized using 1,3,5-tri(1H-imidazole-1-yl)benzene (timb) as a ligand. It was found that CUST-577 exhibited an excellent proton conductivity of 8.9 × 10-3 S cm-1 at 80 °C and 98% RH (relative humidity), proving that CUST-577 was conducted by protons. In addition, CUST-577 also had a greater H2O2 decomposition ability, thereby improving the longevity of fuel cells. In a three-electrode system, CUST-577 displayed a specific capacitance (Cs) value of 308 F g-1 at a current density of 0.15 A g-1, with a capacitance retention of 88.3% after 2000 cycles. Since the proton-conductive electrolyte can deliver protons for the redox reaction of various pseudocapacitor (PC) electrode materials, CUST-577 may be a promising polyacid-based proton conductor material and PC electrode material.