Studies have established a link between exposure to fine particles (PM2.5) and mortality in infants and children. However, few studies have explored the association between post-birth exposure to PM2.5 and under-5 mortality. We conducted a scoping review to identify relevant epidemiological evidence on the association between post-birth ambient PM2.5 exposure and under-5 mortality. We searched PubMed and Web of Science for articles published between 1970 and the end of January 2022 that explicitly linked ambient PM2.5 and under-5 mortality by considering the study area, study design, exposure window, and child age. Information was extracted on the study characteristics, exposure assessment and duration, outcomes, and effect estimates/findings. Ultimately, 13 studies on infant and child mortality were selected. Only four studies measured the effect of post-birth exposure to PM2.5 on under-5 mortality. Only one cohort study mentioned a positive association between post-birth ambient PM2.5 exposure and under-5 mortality. The results of this scoping review highlight the need for extensive research in this field, given that long-term exposure to ambient PM2.5 is a major global health risk and child mortality remains high in some countries.