Deterioration of the skin barrier function causes symptoms such as allergies because various chemical substances may enter the human body. Quantitative evaluation of the thickness and water content of the stratum corneum is useful as a measure of the skin barrier function in domains such as dermatology, nursing science, and cosmetics development. The stratum corneum is responsible for most of the skin barrier function, and two factors—the thickness and water content of the stratum corneum—are thus important. In this paper, the stratum corneum is regarded as a parallel model of resistance and capacitance. From measurements of the electrical impedance of the skin, we propose a new model for simultaneous estimation of the thickness and water content of the stratum corneum conventionally measured by a confocal laser scanning microscope and a confocal Raman spectrometer, respectively, and we discuss the results of the measurements. The electrical impedance of the skin was measured using a device that we developed. The measurement began 3 seconds after the electrodes on the measurement head of the device came into contact with the skin, and parameters including the impedance, which was obtained by applying an alternating current signal at two frequencies, were measured. We measured the thickness and water content of the stratum corneum using confocal laser microscopy and confocal Raman spectroscopy, respectively; investigated the relationship of the thickness and water content of the stratum corneum with the electrical impedance of the skin; and established a new potential model for estimating the thickness and water content of the stratum corneum from the parallel resistance and capacitance. The correlation coefficients of the verification data were 0.931 and 0.776, respectively; and the root-mean-squared error of the thickness of the stratum corneum was 2.3 µm, while the root-mean-squared error of the water content at the surface of the stratum corneum was 5.4 points. These findings indicate the feasibility of quantitative evaluation of the thickness and water content of the stratum corneum by measuring skin electrical impedance.