Surging incidents of air quality-related public health hazards, and environmental degradation, have prompted the global authorities to seek newer avenues of air quality monitoring, especially in developing economies, where the situation appears most alarming besides difficulties around ‘adequate’ deployment of air quality sensors. In the present narrative, we adopt a systematic review methodology (PRISMA, Preferred Reporting Items for Systematic reviews and Meta-Analyses) around recent global literature (2002–2022), around moss-based passive biomonitoring approaches which might offer the regulatory authorities a complementary means to fill ‘gaps’ in existing air quality records. Following the 4-phased search procedure under PRISMA, total of 123 documents were selected for review. A wealth of research demonstrates how passive biomonitoring, with strategic use of mosses, could become an invaluable regulatory (and research) tool to monitor atmospheric deposition patterns and help identifying the main drivers of air quality changes (e.g., anthropogenic and/or natural). Besides individual studies, we briefly reflect on the European Moss Survey, underway since 1990, which aptly showcases mosses as ‘naturally occurring’ sensors of ambient air quality for a slew of metals (heavy and trace) and persistent organic pollutants, and help assessing spatio-temporal changes therein. To that end, we urge the global research community to conduct targeted research around various pollutant uptake mechanisms by mosses (e.g., species-specific interactions, environmental conditions, land management practices). Of late, mosses have found various environmental applications as well, such as in epidemiological investigations, identification of pollutant sources and transport mechanisms, assessment of air quality in diverse and complex urban ecosystems, and even detecting short-term changes in ambient air quality (e.g., COVID-19 Lockdown), each being critical for the authorities to develop informed and strategic regulatory measures. To that end, we review current literature and highlight to the regulatory authorities how to extend moss-based observations, by integrating them with a wide range of ecological indicators to assess regional environmental vulnerability/risk due to degrading air quality. Overall, an underlying motive behind this narrative was to broaden the current regulatory outlook and purview, to bolster and diversify existing air quality monitoring initiatives, by coupling the moss-based outputs with the traditional, sensor-based datasets, and attain improved spatial representation. However, we also make a strong case of conducting more targeted research to fill in the ‘gaps’ in our current understanding of moss-based passive biomonitoring details, with increased case studies.