Cyclic volatile methyl siloxanes (cVMSs) and benzene series compounds have attracted increasing attention because they are associated with various adverse health effects. In this study, we developed and validated a novel passive air sampling method (PAS), using Tenax-TA as the sorbent, to measure the concentrations of cVMSs (D4, D5, and D6) and benzene series compounds simultaneously in indoor air. The uptake rates (R), which were calibrated side-by-side by an active air sampling method (Tenax-TA-AAS), ranged from 0.10 to 0.56 mL min-1 depending on chemicals, and the R of the TD tube with Tenax-TA was controlled by the sampler material-side and not the air-side. The passive sampling efficiency (PSE) of styrene and m,p-xylene was close to 1. Based on Pearson correlation analysis, a negative correlation was found between the molecular weight of compounds and their uptake rates. Furthermore, the calibrated Tenax-TA-PAS method was used to quantify cVMSs and benzene series compounds in a living room and an office environment in the urban area of Dalian, China. The concentrations of toluene were the highest in both the living room (10.4 μg m-3) and office (7.02 μg m-3) among the target compounds.