It has been demonstrated that human exposure to polybrominated diphenyl ethers (PBDEs) might be associated with several adverse health effects. Dietary and microenvironmental sources are considered to be the main routes of PBDEs exposure. The study aimed to investigate PBDEs in residential indoor and outdoor air and further to assess the health risks in family members of different ages. Indoor and outdoor air samples from houses in residential areas were simultaneously collected for analysis of BDE-47, 99, 100, 153, 154, 183, 196, 197, 203, 206, 207, 208, and 209 by high-resolution gas chromatography/high-resolution mass spectrometry. PBDE concentrations were non-significantly higher indoors (81.1 pg/m3) than outdoors (42.7 pg/m3) (p = 0.513). For the outdoor air, the mean PBDE level was lower in air outside houses than in air from industrial and urban areas. Levels of Σ14PBDEs and BDE-209 in house indoor air were no higher in Taiwan than other countries. The daily intake of non-dietary PBDEs from house air and dust in Taiwan was highest in the toddlers (1–2 years old; 8.22 ng/kg b.w./day) and lowest in the male adults (≥ 20 years old; 0.562 ng/kg b.w./day) among family members. For Taiwanese, the risks of non-cancer (hazard quotient: HQ) and cancer (cancer risk: R) with neurobehavioral effects of exposure to non-dietary PBDEs in the home environment were assessed to be lower than the critical values of 1.00 and 1.00 × 10–6 for HQs and Rs, respectively. In conclusion, levels of indoor PBDEs and non-dietary daily intake were found to be low in home environments in Taiwan. This result suggests that PBDEs in the home environment are not harmful to family members from the newborn to the elderly if we only consider the neurobehavioral effects.