In South Asia, combustion of solid fuel for residential heating and cooking is a major emission source of particulate-phase polycyclic aromatic hydrocarbons (p-PAHs), a potent carcinogen for human health. The emission factors (EFs) and source diagnostic ratios of PAHs currently used in regional inventory models have been estimated from controlled laboratory tests, which do not accurately reflect real-world combustion scenarios observed in rural Indian households. Consequently, the health effects associated with p-PAH levels in indoor and ambient air could be severely underestimated and undervalued. We performed a nationwide study across ten different states in the Indian subcontinent to evaluate the EFs and source diagnostic ratios of sixteen U.S. Environmental Protection Agency (EPA) identified high priority p-PAHs emitted from residential solid biomass combustion. Our estimated average annual EFs were 2.4–18.3 fold higher than those reported from previous laboratory-based investigations. Carcinogenic toxicity analysis shows that combustion of dung cake and coal ball, both widely used residential solid fuels, posed the most risk (80% and 59% respectively) in comparison to other PAHs owing to predominant emission of benzo[a]pyrene. Our findings underscore the importance of improved laboratory testing and field validations as crucial steps toward more accurate emission inventories and better assessment of public health impacts.