A simple and effective cooling device based on a thermoelectric cooler was applied to cool the SPME fiber. The device was used for quantitative extraction of aromatic hydrocarbons in the air. Several factors such as coating temperature, extraction temperature and relative humidity in the laboratory setting were optimized. Comparison of the results between the cold fiber SPME (CF-SPME) and NIOSH 1501 method on standard test atmosphere indicated a satisfactory agreement. The CF-SPME and SPME method were also compared. The results revealed that CF-SPME has the most appropriate outcome for the extraction of aromatic hydrocarbons from the ambient air. The cold fiber SPME technique showed good results for several validation parameters. Under the optimized conditions, the limits of detection (LOD) and the limits of quantification (LOQ) ranged from 0.00019 to 0.00033 and 0.0006 to 0.001 ng ml−1, respectively. The intra-day relative standard deviation (RSD) showed ranging from 4.8 to 10.5%.