The accurate determination of the electrical properties of photovoltaic devices is of utmost importance to predict and optimize their overall optoelectronic performance. For example, the minority carrier lifetime and the carrier diffusion length have a strong relationship with the carrier recombination rate. Additionally, parasitic resistances have an important effect on the fill factor of a solar cell. Within this context, the alternating current (AC) and direct current (DC) electrical characteristics of Si-based metal–insulator–semiconductor (MIS) Schottky barrier diodes with the basic structure Al/Si/TiO2/NiCr were studied, aiming at using them as photovoltaic devices. The basic diode structure was modified by adding nanostructured porous silicon (nanoPS) layers and by infiltrating silver nanoparticles (AgNPs) into the nanoPS layers, leading to Al/Si+nanoPS/TiO2/NiCr and Al/Si+nanoPS+AgNPs/TiO2/NiCr structures, respectively. The AC electrical properties were studied using a combination of electrochemical impedance spectroscopy and Mott–Schottky analysis, while the DC electrical properties were determined from current–voltage measurements. From the experimental results, an AC equivalent circuit model was proposed for the three different MIS Schottky barrier diodes under study. Additionally, the most significant electrical parameters were calculated. The results show a remarkable improvement in the performance of the MIS Schottky barrier diodes upon the addition of hybrid nanoPS layers with embedded Ag nanoparticles, opening the way to their use as photovoltaic devices.