Solid-phase microextraction coupled with gas chromatography and mass spectrometry (SPME-GC-MS) was developed for the study of interactions between polycyclic aromatic hydrocarbons (PAHs) and dissolved organic matter (DOM). After the determination of the best conditions of extraction, the tool was applied to spiked water to calculate the dissolved organic carbon water distribution coefficient (K(DOC)) in presence of different mixtures of PAHs and Aldrich humic acid. The use of deuterated naphthalene as internal standard for freely dissolved PAH quantification was shown to provide more accuracy than regular external calibration. For the first time, K(DOC) values of 18 PAHs were calculated using data from SPME-GC-MS and fluorescence quenching; they were in agreement with the results of previous studies. Competition between PAHs, deuterated PAHs and DOM was demonstrated, pointing out the non-linearity of PAH-DOM interactions and the stronger interactions of light molecular weight PAHs (higher K(DOC) values) in absence of high molecular weight PAHs.