Nano-porous silicon (PSi) layers have been prepared by electrochemical etching of (100) Si wafer in the mixture of ethanol (C2H5OH) and hydrofluoric acid (HF). The evolution of morphology of PSi as a function of current density was estimated using the image j and WSxM software’s based on the related SEM images. The electrochemical properties of PSi were investigated using the electrochemical impedance spectroscopy (EIS). The results verified that the estimated charge transfer resistance (Rct) of fabricated PSi was found to increase with the current density from 2.2 kΩ at 10 mA cm−2 to 5.2 kΩ at 30 mA cm−2, due to increase the depth of the silicon nanopores. Additionally, the paper deals with an electrochemical sensing device based on oxide layer covered on PSi nanostructure used to detect ethanol molecules that uses an EIS. The oxide/PSi nanostructure sensor exhibited high response towards ethanol detection, it was estimated about 79.2% at 20 min. It was also verified with the highest sensitivity, 77 μA μM−1 and lower detection limit of 2.4 μM obtained from the chronoamperometric technique. Further, the interference of ethanol on the PSi was studied by regression analysis using the calibration interval.