Monitoring Hg2+ levels in aqueous environments is crucial to assess the potential methylmercury contamination via bacterial conversion, however, existing methods often require extensive sample treatment and expensive equipment. To mitigate this issue, this study examines the synthesis and application of three naphthalimide-based compounds, with significant fluorescent and solvatochromic behavior (C1, C2, and C3). Compounds C1 and C2 demonstrated a strong affinity for Hg2+ metal ions, with C2 showing selectivity and a strong antibacterial profile, particularly against S. aureus (MIC50 (C2) = 0.01 µg/mL). Moreover, these compounds were incorporated into three polymeric matrices, namely polyvinyl chloride (PVC), poly (methyl methacrylate-co-methacrylic acid) (PMMMA), and Starch, allowing for the development of solid-support sensors/surfaces with a strong antibacterial profile, highlighting the inherent dual-functionality of the compounds. Interestingly, the C2-doped Starch biopolymer detected low concentrations of Hg2+ ions, such as 23 nM in tap water (value within the WHO standards for drinking water), through a rapid spectroscopic evaluation without sample treatment. This biopolymer was generated via a sustainable, green-chemistry-oriented, temperature-dependent water/Starch synthetic route, without the addition of plasticizers and any associated ecotoxicity. The study used sustainable methods for environmental monitoring and antibacterial applications, advancing material science to offer effective, accessible, and eco-friendly solutions for detecting and mitigating mercury pollution and bacterial contaminations, enhancing environmental and health safety.