Exploring the effects of different types of PM2.5 is necessary to reduce associated deaths, especially in low- and middle-income countries (LMICs). Hence we determined types of ambient PM2.5 before exploring their effects on under-five and maternal mortality in Africa. The spectral derivate of aerosol optical depth (AOD) from Moderate Resolution Imaging Spectroradiometer (MODIS) products from 2000 to 2015 were employed to determine the aerosol types before using Generalized Linear and Additive Mixed-Effect models with Poisson link function to explore the associations and penalized spline for dose-response relationships. Four types of PM2.5 were identified in terms of mineral dust, anthropogenic pollutant, biomass burning and mixture aerosols. The results demonstrate that biomass PM2.5 increased the rate of under-five mortality in Western and Central Africa, each by 2%, and maternal mortality in Central Africa by 19%. Anthropogenic PM2.5 increased under-five and maternal deaths in Northern Africa by 5% and 10%, respectively, and maternal deaths by 4% in Eastern Africa. Dust PM2.5 increased under-five deaths in Northern, Western, and Central Africa by 3%, 1%, and 10%, respectively. Mixture PM2.5 only increased under-five deaths and maternal deaths in Western (incidence rate ratio = 1.01, p < 0.10) and Eastern Africa (incidence rate ratio = 1.06, p < 0.01), respectively. The findings indicate the types of ambient PM2.5 are significantly associated with under-five and maternal mortality in Africa where the exposure level usually exceeds the World Health Organization’s (WHO) standards. Appropriate policy actions on protective and control measures are therefore suggested and should be developed and implemented accordingly.