Abstract This work examines the physical and chemical interactions between the polar and nonpolar solvents and the surface of the MCM‐41 material, which serves as the isolating layer, employing sensing capacitance‐voltage measurements with a Metal‐Insulator‐Semiconductor (MIS) capacitor. It was observed that the MCM‐41 surface is more sensitive to methanol, which is a protic solvent, than to other nonpolar solvents like chloroform, according to the data. Furthermore, by analyzing the interaction of the methanol with the surface of MCM‐41 as a function of the applied field, the electron transfer, and the orientation of the solvent molecule, DFT Calculations using the Siesta simulation software enable us to assess this sensitivity. Based on the performance of MCM‐41 as the insulator in the MIS capacitor, MCM‐41 has a strong potential for the creation of high‐sensitivity sensors for solvent detection avoiding the functionalization process.