Hydrothermal synthesis was used to create four different POM-based compounds, namely {[Co(Hptpm)2(β-Mo8O26)0.5(ξ-Mo8O26)0.5]}·H2O (1), [Co(Hptpm)2(δ-Mo8O26)]·H2O (2), [Co(Hptpm)2(β-Mo8O26)] (3) and [Zn(Hptpm)2(β-Mo8O26)] (4) (ptpm = 4-[3-(3-pyridine-2-yl-[1,2,4]triazol-4-yl)-propyl]-morpholine). 1-4 containing different octamolybdate isomers were characterized. Compounds 1-4 showed good electrochemical performance and can be utilized as bifunctional sensors for NO2-, H2O2, Cr(VI) and Fe(III). Taking compound 1 as an example, the detection limits are 0.081 μM for NO2-, 0.072 μM for H2O2, 0.054 μM for Cr(VI) and 0.063 μM for Fe(III), respectively. Compounds 1-4 have good capacitance. Moreover, compounds 1-4 also show good adsorption properties for organic cationic dyes. The cationic dyes include methylene blue (MB), crystal violet (CV) and neutral red (NR). In addition, 1-4 have excellent characteristics that can reduce Cr(VI) to Cr(III) by photocatalytic technology. Within 30 min, the reduction rates were 95.85% for 1, 93.99% for 2, 90.29% for 3 and 88.18% for 4.