<p>This study reports health risk assessment of PM<sub>1</sub>-bound carcinogenic hexavalent chromium [Cr(VI)] from central part of Indo-Gangetic plain (IGP) (PM<sub>1</sub>: particulate matter with aerodynamic diameter ≤1µm). Cr(VI) concentration has been estimated utilizing spectrophotometer with a modified novel method. Average ratio of Cr(VI)/Cr<sub>T</sub> was 0.39 ± 0.07 (Cr<sub>T</sub>: Total chromium) in the central IGP (Kanpur). Our study reports that mass fraction of Cr(VI) averaging at 0.39 is ∼3 times higher than that assumed conventionally [Cr(VI)/Cr<sub>T</sub>: 1/7]. Cancer risk assessment has been performed by assessing excess cancer risk (ECR) for the Cr(VI). ECR determined due to Cr(VI) was 57 and 14.3 (in one million) for adults and children, respectively. Our study suggests that risk due to Cr(VI) reported in previous studies were being underestimated by a factor of three. The Cr(VI)/Cr<sub>T</sub> average ratio of 0.39 determined in this study was utilized to calculate risk assessment due to Cr(VI) from other locations in the IGP. Owing to large population of India (∼125 million), the cancer risk due to Cr(VI) inhalation itself would become very significant. Thus, future research should focus on metal speciation of PM-bound samples from different locations to better constraint the toxicological risk assessment on a regional-to-global scale.</p