Exposure assessment in children is a complex process. The silicone wristband, a passive sampling method, has promising applicability in exposure studies in children. We compared the level of nicotine in a silicone wristband to a passive nicotine air monitor worn by children for 7 days. Children (n = 52) in San Diego County were recruited who were exposed to tobacco smoke and/or vapor from electronic cigarettes (EC), as well as children who lived in nonsmoking homes. Caregivers were interviewed to obtain reported measures of the child’s exposure. Nicotine analysis was by liquid chromatography with triple quadrupole mass spectrometry and isotope dilution (LC-MS/MS). Nicotine in the silicone wristband was significantly correlated with personal air nicotine (r2 = 0.741, p < 0.001). Both the air monitors and silicone wristbands discriminated between nonsmoker, EC and smoker groups, but the silicone wristbands were more sensitive, with 100 percent nicotine detection and a greater dynamic range. Silicone wristbands show promise to detect exposures to nicotine in children when compared to the more conventional exposure assessment method applying passive nicotine air samplers.