This paper aims to characterize Non-Melanoma malignancies and their corresponding benign conditions in ex-vivo/in-vivo tissue environments to study the feasibility of microwave techniques for skin cancer detection.The dielectric dataset is developed across the frequency band 1 to 14 GHz using Keysight slim-form and RG405 probe characterization systems. The acquired reflection data captured by the systems is converted to dielectric values using the Open-Water-Short and Open-Water-Liquid calibration methods, respectively. Furthermore, the impact of anaesthesia application during skin excision procedure on ex-vivo dielectric data is investigated.The observations suggest that the dielectric properties (DPs) of excised skin lesions may not accurately represent actual tissue properties as they vary significantly (Dielectric Constant Contrast = 30.7%, Loss-Factor Contrast = 66.6%) compared to pre-excision conditions. In-vivo dielectric data analysis indicates that when compared to healthy skin, malignant Basal Cell Carcinoma presents increased DPs (dielectric constant & loss factor) of (24.8 & 38.6 %), respectively. On the other hand, for malignant Squamous Cell Carcinoma and pre-malignant Actinic Keratosis, the measured results show decreased DPs (dielectric constant & loss factor) accordingly by (19.4 & 18.2 %) and (19.2 & 27.9 %). The corresponding benign lesions have less than 13 % dielectric contrast compared to healthy skin across the tested band.The significant contrasts between in-vivo healthy and cancerous skin DPs strongly suggest the viability of the microwave band for skin cancer detection.The research finding of this study would be critical in developing a portable electromagnetic system for skin cancer detection.