Octamethylcyclotetrasiloxane (D4) and decamethylpentasiloxane (D5) are used as ingredients for personal care products (PCPs). Because of the use of these PCPs, consumers are exposed daily to D4 and D5. A sensitive analytical method was developed for analysis of D4 and D5 in end-exhaled air by thermal desorption gas chromatography mass spectrometry (TD-GC-MS), to determine the internal dose for consumer exposure assessment. Fifteen consumers provided end-exhaled air samples that were collected using Bio-VOC breath samplers and subsequently transferred to automatic thermal desorption (ATD) tubes. Prior to use, the ATD tubes were conditioned for a minimum of 4 h at 350 °C. The TD unit and auto sampler were coupled to a GC-MS using electron ionization. Calibration was performed using 0-10 ng/μL solutions of D4/D5 and (13)C-labeled D4/D5 as internal standards. The ions monitored were m/z 281 for D4, 355 for D5, 285 for (13)C-labeled D4, and 360 for (13)C-labeled D5. The addition of internal standard reduced the coefficient of variation from 30.8% to 9.5% for D4 and from 37.8% to 12.5% for D5. The limit of quantification was 2.1 ng/L end-exhaled air for D4 and 1.4 ng/L end-exhaled air for D5. With this method, cyclic siloxanes (D4 and D5) can be quantified in end-exhaled air at concentrations as low as background levels observed in the general population.