Background/Objectives: This study aimed to perform a comparative analysis of the original Viagra® product and sildenafil-containing tablets obtained from illegal sources (the darknet). Specifically, the analyzed material consisted of samples seized by Polish law enforcement authorities from unverified vendors operating within the Central European darknet market. The study utilized thermal methods, specifically Thermogravimetry (TG), Derivative Thermogravimetry (DTG), and calculated Differential Thermal Analysis (c-DTA), as well as colorimetric analysis based on the International Commission on Illumination (CIE) L*a*b* system. Methods: Thermal analyses enabled the assessment of the thermal stability of the tested samples, identification of characteristic stages of thermal decomposition, and determination of differences in thermal behavior between the pure substance, the original preparation, and darknet samples. In turn, color measurements in the CIE L*a*b* space allowed for an objective comparison of tablet appearance and determination of the degree of color similarity to the original product. Results: The obtained results showed that only a few samples (V1, V3, V4, V6, V8) exhibited features similar to the original Viagra®, both in terms of thermal profile and color. Most of the tested tablets were characterized by significant variability in physicochemical properties, indicating a lack of quality control and inconsistency in formulation. Samples V2 and V7 deviated particularly strongly—both thermally and visually—suggesting that they might not contain the original active substance or contained it in a different chemical form. Conclusions: The use of combined thermal and colorimetric methods proved to be an effective tool in the identification of counterfeit pharmaceutical products, enabling simultaneous evaluation of their composition and authenticity. The results confirm the validity of employing integrated physicochemical analyses for the detection of falsified medicines present on the illegal market.
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