At present, indoor VOCs pollution was widespread concerned. However, for human emission of VOCs, fundamental data was in shortage in the field of indoor air quality (IAQ). In this study, 11 male subjects without smoking habit, 12 female subjects without smoking habit and 12 male subjects with smoking habit were selected. Their samples of exhaled breath were collected and concentrated by sampling bags and sorbent tubes, and analyzed by gas chromatography-mass spectrometry (GC / MS). 135 VOCs were observed in all 35 samples. An average breath sample contained 79.7 VOCs (SD16.2, range 43–110) were obtained, 12 VOCs were observed in all 35 subjects. Furthermore, quantitive analysis of main indoor pollutants: benzene, toluene, xylene and naphthalene were performed, as well as TVOC. The effect of gender was found not as strong factor as the effect of smoking habit. Exhaled VOCs of female subjects were of higher concentration than male subjects. Exhaled VOCs of subjects with smoking habits were more diverse and of higher concentration.