Polyoxometalates (POMs) are attractive materials for various applications such as energy storage, catalysis and medicine. Here, Co and Ni-based POMs are chemically synthesized and characterized by X-ray diffractometer (XRD) and Fourier transform infrared spectroscopies (FT-IR) for structural characterization. While the morphological behaviors are analyzed by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and atomic force microscopy (AFM), the optical properties are investigated by UV-Vis spectrometer. Electrochemical characterizations are carried out by cyclic voltammetry to determine oxidation levels of the metal centers in the POMs. The CoPOM and NiPOM are inserted in between the Al metal and p-Si semiconductor to obtain Al/CoPOM/p-Si and Al/NiPOM/p-Si Schottky-type photodetector devices. Current-voltage (I–V) and current-transient (I–t) measurements are employed to understand the electrical properties of the Al/CoPOM/p-Si and Al/NiPOM/p-Si devices under dark and various light power intensities. The devices exhibit phototransistor like I–V characteristics in forward biases due to having POMs active layers. Various device parameters are extracted from the I–V measurements and discussed in details. I–t measurements are performed to determine various detector parameters such as responsivity and specific detectivity values for under 2 V and zero biases. The Al/CoPOM/p-Si and Al/NiPOM/p-Si Schottky-type photodetector devices can be employed in optoelectronic applications.