The typical large specific surface area and high reactivity of nanostructured porous silicon (nanoPS) make this material very suitable for the development of sensors. Moreover, its biocompatibility and biodegradability opens the way to the development of biosensors. As such, in this work the use of nanoPS in the field of electrical biosensing is explored. More specifically, nanoPS-based devices with Al/nanoPS/Al and Au-NiCr/nanoPS/Au-NiCr structures were fabricated for the electrical detection of glucose and Escherichia Coli bacteria at different concentrations. The experimental results show that the current-voltage characteristics of these symmetric metal/nanoPS/metal structures strongly depend on the presence/absence and concentration of species immobilized on the surface.