This study modified a passive sampling technique similar to the US EPA Method 325 A/B method but extended to include more toxic volatile organic compounds (VOCs) under varied climate conditions to enhance field applicability. A mixing chamber was built to determine uptake rates (Us) for the target compounds. It was found that the Us of 27 air toxics previously reported in the literature agreed reasonably well with our findings within 18%, thus proving the chamber's integrity. To broaden the compound coverage, both Carbopack X and Carboxen 569 were studied for a suite of toxic VOCs to meet stringent quality control (QC) criteria of correlation coefficients (R-square), method detection limits (MDL), back diffusion (BD), storage stability, as well as a wide range of climate conditions in temperature and humidity. After excluding the species that failed to pass any of the QC criteria, Carbopack X was found to fit 50 air toxics, whereas Carboxen 569 held 37. After excluding the overlapped species, 61 toxic VOCs can be determined with robust Us for a broad range of climate conditions when the two sorbents are used in pairs. A one-week field measurement was conducted to compare with the online thermal desorption gas chromatography-mass spectrometry (TD-GC-MS) with hourly data resolution. The field passive sampling showed comparable results to the means of the online hourly measurements, despite the high variability of selected target compounds, such as toluene from 0.3 ppbv as the 5th percentile to the maximum of about 80 ppbv. Passive sampling clearly demonstrated the ability to smooth out concentration variability and thus the time-averaging strength of toxic VOCs, revealing its ideal role as an exposure monitor over time. The passive sampling method can be more desired than active sampling or online methods when the aim is simply the knowledge of prolonged time-averaged concentrations.