A new method was developed for collecting, identifying and quantifying contaminants in hot process gas streams using time-weighted average (TWA) passive sampling with retracted solid-phase microextraction (SPME) and gas chromatography. The previous lab scale proof-of-concept with benzene was expanded to include the remaining major tar compounds of interest in syngas: toluene, styrene, indene, and naphthalene. The new method was tested on high T (⩾100 °C) process gas from a pilot-scale fluidized bed gasifier feeding switchgrass and compared side-by-side with conventional impingers-based method. Fourteen additional compounds were identified, representing 40–60% improvement over the conventional method’s detection capacity. Differences between the two methods were 1–20% and as much as 40–100% depending on the sampling location. Compared to the inconsistent conventional method, the SPME-TWA offered a simplified, solvent-free approach capable of drastically reducing sampling and sample preparation time and improving analytical reliability. The improved sensitivity of the new method enabled identification and quantification of VOCs beyond the capability of the conventional approaches, reaching concentrations in the ppb range (low mg/m3). RSDs associated with the TWA-SPME were <10%, with most lab-based trials yielding <2%. Calibrations were performed down to the lowest expected values of tar concentrations in ppb ranges (low mg/N m3, with successful measurement of tar concentrations at times >4000 ppm (up to 10 g/N m3). The new method can be a valid alternative to the conventional method for light tar quantification under certain conditions. The opportunity also exists to exploit TWA-SPME for process gas streams analysis e.g., pyrolysis vapors and combustion exhaust.