The accelerated pace of industrialization in Central India has resulted in heightened emissions of polycyclic aromatic hydrocarbons, thereby eliciting substantial environmental and public health apprehensions. This investigation assessed the prevalence, spatial variability, and interlinkages between environmental and biological PAH levels in soil, plant, and blood sample collected from prominent industrial locales across Central India with a focus on evaluating potential exposure among industrial workers. In aggregate, 250 samples were subjected to analysis through liquid chromatography and conventional gas chromatography accompanied by tandem mass spectrometry techniques. Soil samples exhibited the highest concentrations of PAHs (0.11–1.58 ppm; mean 0.63 ppm), followed by plant samples (0.05–2.59 ppm; mean 0.77 ppm), whereas blood samples exhibited detectable concentrations (51.81–29712.66 ppb; mean 1059.74 ppb), indicating potential human exposure. Spatial analysis identified the Siltara Area and Korba Industrial Area as the primary contamination hotspots. Correlation analysis revealed a weak negative relationship between soil and plant samples (r = -0.28) and a stronger negative association between plant and blood samples (r = -0.73), suggesting complex exposure pathways. Risk evaluation utilizing toxic equivalency concentrations, incremental lifetime cancer risk, and hazard index demonstrated that non-carcinogenic risks were confined to acceptable thresholds; however, marginally elevated carcinogenic risks were identified in the Siltara region. The detection of low-molecular-weight PAHs in blood samples may suggest prospective occupational exposure among industrial workers, aligning with occupational safety concerns. These observations emphasize the necessity for sustained environmental monitoring and occupational health surveillance across industrial areas in Central India.