α-Keggin POM based compounds (KL1-KL3) were synthesized from the reactions between imine ligands (HL1-HL3) and α-Keggin-type polyoxometalates and their structures were characterized by various instrumental methods. In addition to other techniques, 1H(13C)NMR methods were also used in the characterization of the azo imine organic ligands (HL1-HL3). After the Cu2+ and Pt2+ complexes of the hybrid compounds were synthesized and characterized, their photophysical, electrochemical and antimicrobial properties were investigated. The compounds showed activity against penicillium spp. On the other hand, the KL2 POM compound showed the highest antibacterial activity. In the UV-vis spectra of the KL1, KL2 and KL3 POM based compounds in DMF solution, the charge transfer transitions (CT) are observed in the range of 458−453 nm, while ligand-centered π−π* transitions are in the range of 333−316 nm. Among the complexes of hybrid compounds, only the emission values of the KL1Cu complex in the DMF medium and in the solid state shifted to shorter wavelengths. It was determined that some of the POM based metal complexes showed only metal-centered electrochemical behaviors. In addition, the thermal stability of all compounds was also investigated.