Objective: To assess the impact of different smoking behaviors of caregivers on environmental tobacco smoke (ETS) exposure in children aged 5–6 years in Changsha, China. Methods: We conducted a cross-sectional, random digit-dial telephone survey of caregivers (n = 543) between August and October 2013. Caregivers’ smoking behaviors were collected by a questionnaire. Exposure assessment was based upon determination of urinary cotinine levels in children employing gas chromatography–triple quadrupole mass spectrometry (GC-MS/MS). Results: In children not living with a smoker, children living with one smoker, and children living with more than one smoker at home, median urinary cotinine concentrations (ng/mL) were 0.72, 2.97, and 4.46, respectively. For children living with one smoker, median urinary cotinine levels of children exposed to ETS were associated with caregiver smoking behaviors, i.e., if a caregiver consumed more cigarettes (>20 compared with ≤10; 7.73 versus 2.29 ng/mL, respectively). Conclusions: The magnitude of ETS exposure in children is correlated with the smoking behaviors of the caregiver. Counseling for smoking cessation and educational interventions are needed urgently for smoking caregivers to increase their awareness about ETS exposure and to encourage smoking cessation at home or to take precautions to protect children’s health.