Background: Conventional methods for assessing exposure to environmental tobacco smoke rely mainly on questionnaires and biomarkers with short half-lives, such as urinary cotinine. In contrast, oral mucosal pigmentation may represent a visible, non-invasive biomarker of chronic exposure. However, its clinical and policy relevance, as well as its validity for screening purposes, remain insufficiently established. Aim: To summarize the evidence on the association between exposure to environmental tobacco smoke and oral mucosal pigmentation and to assess some confounding factors. Materials and Methods: We synthesized findings from observational studies that examined the association between environmental tobacco smoke exposure and oral mucosal pigmentation across all age groups. International electronic databases, including PubMed, Embase, Web of Science, and Scopus, were searched. Data were extracted on exposure–response relationships, measurement instruments, anatomical distribution of pigmentation, confounding by physiological pigmentation, and biochemical validation. The quality of included studies was assessed using the Mixed Methods Appraisal Tool (MMAT). A narrative synthesis was conducted, focusing on the biological plausibility of the biomarker, standardization of measurement, and its potential implications for screening and tobacco control policy. Results: Thirteen observational studies from seven countries, involving a total of 3,284 participants, met the inclusion criteria. Four studies reported a statistically significant association between duration of exposure and severity of pigmentation, while one cohort study showed that urinary cotinine levels increased with age among children. The Gingival Pigmentation Index and the Dummett Oral Pigmentation Index were the most commonly used assessment tools; however, methodological heterogeneity limited direct comparability across studies. The anterior gingiva was the most frequently affected anatomical site. Only a limited number of studies adequately controlled for physiological pigmentation, and skin color was identified as an important confounding factor. The pooled odds ratio was 2.35; however, the certainty of evidence was low due to the observational nature of the included studies. Conclusion Oral mucosal pigmentation may serve as a potential biomarker of long-term exposure to environmental tobacco smoke. Nevertheless, standardized assessment protocols, adequate control for physiological pigmentation, and validation against “gold-standard” biomarkers are required. If validated, this marker could be used for rapid identification of high-risk groups and incorporated into tobacco control policies.