Background: Pelotherapy is the traditional procedure of applying curative muds on the skin’s surface—shown to have a positive effect on the human body and cure illnesses. The effect of pelotherapy is complex, functioning through several mechanisms, and depends on the skin’s functional condition. The current research objective was to develop a methodology and electrodes to assess the passage of the chemical and biologically active compounds of curative mud through human skin by performing electrical bioimpedance (EBI) analysis. Methods: The methodology included local area mud pack and simultaneous tap water compress application on the forearms with the comparison to the measurements of the dry skin. A custom-designed small-area gold-plated electrode on a rigid printed circuit board, in a tetrapolar configuration, was designed. A pilot study experiment with ten volunteers was performed. Results: Our results indicated the presence of an effect of pelotherapy, manifested by the varying electrical properties of the skin. Distinguishable difference in the measured real part of impedance (R) emerged, showing a very strong correlation between the dry and tap-water-treated skin (r = 0.941), while a poor correlation between the dry and mud-pack-treated skin (r = 0.166) appeared. The findings emerged exclusively in the frequency interval of 10 kHz …1 MHz and only forR. Conclusions: EBI provides a promising tool for monitoring the variations in the electrical properties of the skin, including the skin barrier. We foresee developing smart devices for promoting the exploitation of spa therapies.