RATIONALE The gold standard for monitoring volatile organic compounds (VOCs) is gas chromatography/mass spectrometry (GC/MS). However, in many situations, when VOC concentrations are at the ppmv level, there are complicating factors for GC/MS. Selected ion flow tube mass spectrometry (SIFT‐MS) is an emerging technique for monitoring VOCs in air. It is simpler to use and provides results in real time. METHODS Three different experiments were used for the comparison. First SIFT‐MS was applied to monitor the concentrations of 25 VOCs in a mixture at concentrations up to 1 ppmv using only a generic database for known kinetic data of three reagent ions (H 3 O + , NO + and O 2 + ) with each VOC. In experiment 2, a side‐by‐side comparison was made of 17 VOCs at concentrations between 1 ppmv and 5 ppbv after small corrections had been made to the SIFT‐MS kinetic data. In a third experiment, a side‐by‐side comparison examined two groups of samples received for commercial analysis. RESULTS In experiment 1, 85% of the VOC concentrations were within 35% of their stated values without any calibration of the SIFT‐MS instrument. In experiment 2, the two techniques yielded good correspondence between the measured VOC concentrations. In experiment 3, good correlation was found for VOCs from three of the samples. However, interferences from some product ions gave over‐reported values in one sample from the SIFT‐MS instrument. CONCLUSIONS These three experiments showed that GC/MS was better suited to monitoring samples containing large numbers of VOCs at high concentrations. In all other applications, SIFT‐MS proved simpler to use, was linear with concentration over a much wider concentration range than GC/MS and provided faster results. Copyright © 2013 John Wiley & Sons, Ltd.