Airborne volatile organic compounds (VOCs) and semi-volatile organic compounds (SVOCs) are commonly quantitated by collecting the analytes on solid sorbent tubes or passive air samplers, followed by solvent extraction and instrumental analysis, or by grab bag/canister measurements. We report herein a user-friendly sampling method by breathing through polyurethane foam (PUF) face masks to collect airborne VOCs and SVOCs for chemical analysis. Specifically, dibasic esters, phthalate esters, polycyclic aromatic hydrocarbons, linalool, and nicotine trapped on PUF masks were quantitated by gas chromatography-mass spectrometry analysis as model VOCs and SVOCs. Results showed that the amount of these model VOCs and SVOCs trapped on PUF masks is proportional to the exposure duration. After cross-validation by parallel sampling using XAD-2 packed sorbent tubes, the method was used to quantitate VOCs and SVOCs in a variety of indoor and outdoor environments with varying air concentrations of analytes, temperature, humidity, and wind speed. Because air pollution is considered a major cause of many human diseases and premature deaths and the developed PUF mask sampling method showed high trapping efficiencies for both VOCs and SVOCs, it is believed that the developed sampling method will find wide application in assessing air pollution-associated disease risks with possible extension to more classes of VOCs and SVOCs when coupled with suitable instrumental detection methods.