The interest in quantitative analysis of biogenic volatile organic compounds (BVOCs) emissions stems from their importance in atmospheric chemistry. In order to compare the most frequently used BVOC measurement techniques, simultaneous on-line PTR-MS and off-line GC-MS data collection was performed on a 3 years old Fagus sylvatica L. tree placed in a growth chamber. Using an internal standard (deuterated toluene) and applying the selective ion mode (SIM) resulted in significant improvements of monoterpene (MT) quantification by TD-GC-MS. PTR-MS quantification of MTs was based on the ion signal at m/z 137. In the course of the experiments the relative contribution of linalool compared to that of MTs was found to be up to 84%. Since this compound has also a PTR-MS signature at m/z 137, quantification of MT emission rates by PTR-MS was disturbed. Comparison of GC-MS and PTR-MS data allowed an estimation of the ratio of the PTR-MS sensitivity for linalool to the one for MTs at m/z 137. This ratio of sensitivities, combined with the information of the relative contribution of linalool to the sum of linalool and MTs obtained by GC-MS, resulted in accurate derivation of the sum of emission rates of linalool and MTs by PTR-MS. The results indicate that fast and on-line PTR-MS measurements of BVOCs are best accompanied by off-line GC measurements to detect possible interferences or to use the additional information for properly quantifying the sum of emission rates of several compounds. © 2010 Elsevier B.V. All rights reserved.