Although short‐duration elevated exposures (peak exposures) to pollutants may trigger adverse acute effects, epidemiological studies to understand their influence on different health effects are hampered by lack of methods for objectively identifying peaks. Secondhand smoke from cigarettes (SHS) in the residential environment can lead to peak exposures. The aim of this study was to explore whether peaks in continuous PM2.5 data can indicate SHS exposure. A total of 41 children (21 with and 20 without SHS exposure based on self‐report) from 28 families in New York City (NY, USA) were recruited. Both personal and residential continuous PM2.5 monitoring were performed for five consecutive days using MicroPEM sensors (RTI International, USA). A threshold detection method based on cumulative distribution function was developed to identify peaks. When children were home, the mean accumulated peak area (APA) for peak exposures was 297 ± 325 hour*µg/m3 for children from smoking families and six times that of the APA from non‐smoking families (~50 ± 54 hour*µg/m3). Average PM2.5 mass concentrations for SHS exposed and unexposed children were 24 ± 15 µg/m3 and 15 ± 9 µg/m3, respectively. The average SHS exposure duration represents ~5% of total exposure time, but ~13% of children's total PM2.5 exposure dose, equivalent to an additional 2.6 µg/m3 per day. This study demonstrated the feasibility of peak analysis for quantifying SHS exposure. The developed method can be adopted more widely to support epidemiology studies on impacts of short‐term exposures.