Air pollution in India is a foremost environmental risk factor that affects human health. This study first investigates the geographical distribution of ambient and household air pollution (HAP) and then examines the associated mortality risk. Data on fine particulate matter (PM2.5) concentration has been extracted from the Greenhouse Gas Air Pollution Interactions and Synergies (GAINS) model. HAP, mortality and socio-demographic data were extracted from the National Family and Health Survey-5, India, 2019-2021. Regression models were applied to see the difference in age-group mortality by different pollution parameters. The districts with PM2.5 concentration above the National Ambient Air Quality Standard (NAAQS) level of 40 mu g/m3 show a higher risk of neonatal (OR-1.86, CI 1.418-2.433), postneonatal (OR-2.04, CI 1.399-2.971), child (OR-2.19, CI 0.999-4.803) and adult death (OR-1.13, CI 1.060-1.208). The absence of a separate kitchen shows a higher probability of neonatal (OR: 1.18, CI 1.074-1.306) and adult death (OR-1.06, CI 1.027-1.088). The interaction between PM2.5 levels above NAAQS and HAP leads to a substantial rise in mortality observed for neonatal (OR 1.19 CI 1.051-1.337), child (OR 1.17 CI 1.054-1.289), and adult (OR 1.13 CI 1.096-1.168) age groups. This study advocates that there is a strong positive association between ambient and HAP and mortality risk. PM2.5 pollution significantly contributes to the mortality risk in all age groups. Children are more vulnerable to HAP than adults. In India, policymakers should focus on reducing the anthropogenic PM2.5 emission at least to reach the NAAQS, which can substantially reduce disease burden and, more precisely, mortality. Air pollution in India poses a significant threat to human health, as explored in this study. Using data from the Greenhouse Gas Air Pollution Interactions and Synergies model and the National Family and Health Survey-5, the research examines both ambient and household air pollution and their impact on mortality risk. Analyzing fine particulate matter (PM2.5) concentration, the study finds that districts exceeding the National Ambient Air Quality Standard (NAAQS) of 40 mu g/m3 face increased mortality risks across all age groups, including neonatal, postneonatal, child, and adult deaths. Additionally, the absence of separate kitchens correlates with higher neonatal and adult mortality rates. The interaction between elevated PM2.5 levels and household air pollution further amplifies mortality risks, particularly among neonates, children, and adults. The study underscores the urgent need for policymakers to mitigate anthropogenic PM2.5 emissions to meet NAAQS standards, which could significantly reduce mortality and disease burden, particularly among vulnerable populations like children. Interaction between PM2.5 levels above National Ambient Air Quality Standard and household air pollution, leads to a substantial rise in mortality observed for all age-groups Districts with PM2.5 levels exceeding the National Ambient Air Quality Standard show an approximately two fold increase in the odds of mortality among children