<p>Polychlorinated biphenyls (PCBs), despite their global ban and phase-out, remain a critical environmental concern in developing nations where evidence of declining concentrations is inconsistent. This review presents the first matrix-based review of PCB contamination in the Indian environment and human populations during the period 1990–2025. A total of 178 references, including peer-reviewed studies and supplementary sources, were systematically evaluated to examine contamination levels, emission sources, and exposure pathways. The analysis reveals major knowledge gaps in trade transparency, long-term monitoring, human health risk assessment, and regulatory enforcement. Historically, PCB contamination in India was linked to imports of PCB-containing equipment and oils, primarily for the power sector. Since the 1990s, however, unintentional emissions from inadequate waste management, informal e-waste recycling, and open burning have become dominant sources. The persistence of mono and non-ortho congeners across environmental matrices raises concerns about ongoing re-emission, accumulation, and chronic human exposure. Although concentrations are often below acute toxicity thresholds, chronic exposures frequently exceed safe limits, especially for vulnerable populations such as children and informal-sector workers. Indian urban atmospheres also show slower rates of PCB decline compared to nations with stricter management frameworks. Limited disposal infrastructure, insufficient data on open and partially closed industrial uses, and uncertainties in trade reporting aggravated by PCBs being grouped under Harmonized System codes further complicate management. India’s evolving regulatory framework under the Stockholm Convention reveals gaps in monitoring and legacy stockpile management, underscoring the need for stronger monitoring, sound waste practices, and comprehensive risk management.</p> Graphical Abstract <p></p>