A method for automated detection and reporting of pesticides in plant materials based on comprehensive two-dimensional GC/time-of-flight MS with library-based detection by software has been developed and validated. Optimum settings for detection parameters such as spectral match threshold and first and second dimension retention time tolerances were assessed with respect to occurrence of false detects and false negatives. Next the method was validated following European Union guidelines established for qualitative screening of pesticides. The validation was largely done in retrospect by using data obtained for spiked samples (235 pesticides, various crops, 0.01-0.2 mg/kg) that had been analyzed previously with routine samples over a period of 18 months. At 0.01 mg/kg, the required 95% confidence level (<5% false negatives) was met for 83 compounds. This increased to 185 compounds at the 0.2 mg/kg level. For a number of pesticides, especially at low levels, it had to be concluded that at this stage the method was not fit-for-purpose to reliably demonstrate the absence of pesticides in samples to be analyzed. On the other hand, the fact that the overall detection rate at 0.01 mg/kg was 71% clearly showed that the method does provide added value for the numerous pesticides that are not covered by quantitative methods because the infrequent occurrence does not justify inclusion in such methods.