In this work, the capability of gas chromatography coupled to time-of-flight mass spectrometry (GC-TOF MS) for quantitative analysis of pesticide residues has been evaluated. A multiclass method for rapid screening of pesticides (insecticides, acaricides, herbicides and fungicides) in fruit and vegetable matrices has been developed and validated, including detection, identification and quantification of the analytes. To this aim, several food matrices were selected: high water content (apples, tomatoes and carrots), high acid content (oranges) and high oil content (olives) samples. The well known QuEChERS procedure was applied for extraction of pesticides, and matrix-matched calibration using relative responses versus internal standard was used for quantification. The sample extracts were analyzed by GC-TOF MS. Up to five ions using narrow window (0.02 Da)-extracted ion chromatograms at the expected retention time were monitored using a target processing method. The most abundant ion was used for quantification while the remaining ones were used for confirmation of the analyte identity. Method validation was carried out for 55 analytes in the five sample matrices tested at three concentrations (0.01, 0.05 and 0.5 mg/kg). Most recoveries were between 70% and 120% with relative standard deviations (RSDs) lower than 20% at 0.05 and 0.5mg/kg. At 0.01 mg/kg, roughly half of the pesticides could be satisfactorily validated due to sensitivity limitations of GC-TOF MS, which probably affected the ion ratios used for confirmation of identity. In the case of olive samples, results were not satisfactory due to the high complexity of the matrix. An advantage of TOF MS is the possibility to perform a non-target investigation in the samples by application of a deconvolution software, without any additional injection being required. Accurate-mass full-spectrum acquisition in TOF MS provides useful information for analytes identification, and has made feasible in this work the discovery of non-target imazalil, fluoranthene and pyrene in some of the samples analyzed.