Human skin acts as a protective barrier, preserving bodily functions and regulating water loss. Disruption to the skin barrier can lead to skin conditions and diseases, emphasizing the need for skin hydration monitoring. The gold-standard sensing method for assessing skin hydration is the Corneometer, monitoring the skin's electrical properties. It relies on measuring capacitance and has the advantage of precisely detecting a wide range of hydration levels within the skin's superficial layer. However, measurement errors due to its front end requiring contact with the skin, combined with the bipolar configuration of the electrodes used and discrepancies due to variations in various interfering analytes, often result in significant inaccuracy and a need to perform measurements under controlled conditions. To overcome these issues, we explore the merits of a different approach to sensing electrical properties, namely, a tetrapolar bioimpedance sensing approach, with the merits of a novel optical sensing modality. Tetrapolar bioimpedance allows for the elimination of bipolar measurement errors, and optical spectroscopy allows for the identification of skin water absorption peaks at wavelengths of 970 nm and 1450 nm. Employing both electrical and optical sensing modalities through a multimodal approach enhances skin hydration measurement sensitivity and validity. This layered approach may be particularly beneficial for minimising errors, providing a more robust and comprehensive tool for skin hydration assessment. An ex vivo desorption experiment was carried out on fresh porcine skin, and an in vivo indicative case study was conducted utilising the developed optical and bioimpedance sensing devices. Expected outcomes were expressed from both techniques, with an increase in the output of the optical sensor voltage and a decrease in bioimpedance as skin hydration decreased. MLR models were employed, and the results presented strong correlations (R-squared = 0.996 and -value = 6.45 × 10), with an enhanced outcome for hydration parameters when both modalities were combined as opposed to independently, highlighting the advantage of the multimodal sensing approach for skin hydration assessment.