GAS CHROMATOGRAPHY coupled to MASS SPECTROMETRY (GC-MS) has been extensively applied for determination of volatile, non-polar, compounds in many applied fields like food safety, environment or toxicology. The wide majority of methods reported use electron IONIZATION (EI), which may result in extensive fragmentation of analytes compromising selectivity and sensitivity. This might also complicate the application of TANDEM MS due to lack of specific/abundant precursor ions. PYRETHROIDs are examples of compounds with this behaviour. In this work the potential of ATMOSPHERIC PRESSURE CHEMICAL IONIZATION (APCI), a softer form of ionisation, combined with GC and a triple quadrupole MASS analyzer was investigated, taking PYRETHROIDs as a case study and their determination in fruit and vegetables as example application. IONIZATION and fragmentation behavior of eight PYRETHROIDs (bifenthrin, cyfluthrin, cypermethrin, permethrin, -cyhalothrin, fluvalinate, fenvalerate and deltamethrin) by APCI were studied. The formation of a highly abundant (quasi) molecular ion was the main goal because of the enhanced selectivity when used as precursor ion in TANDEM MS. The addition of water as a modifier was tested to promote the generation of protonated molecules, resulting in notable improvement of sensitivity and selectivity for most compounds. The excellent detectability (LODs <20 fg achieved) when using APCI combined with state-of-the-art TANDEM MS was demonstrated for real samples. Additionally, matrix effects were evaluated in terms of signal enhancement/suppression. Depending on the matrix, different degrees of suppression were observed, on average reducing the signal in matrix to 55% of that in solvent. The results presented in this paper demonstrate the potential of APCI as new source for GC-MS that could be applied to other analytical problems apart from those illustrated in this work.