In this study, a new analytical methodology was proposed for the simultaneous determination of 16 polycyclic aromatic hydrocarbons (PAH) in leached extracts. This approach consisted of a new configuration based on hollow fiber-microporous membrane liquid–liquid extraction (HF-MMLLE) with palladium nanoparticles (Pd-NPs) impregnated in the pores of the membrane as part of the extraction phase. The analytes were separated and identified by gas chromatography coupled to mass spectrometry (GC–MS). The optimizations of the main extraction and desorption parameters were evaluated using univariate and multivariate strategies. The optimized extraction conditions were achieved with the use of 1-octanol solvent with the Pd-NPs as extraction phase, salt concentration adjusted to 5% (w/v of NaCl), 150 µL of acetonitrile as solvent of desorption, 70 and 30 min of extraction and desorption time, respectively. Satisfactory analytical performance was obtained with correlation coefficients greater than 0.9818, detection and quantification limits of 1.5 and 5.0 ng mL−1, respectively, for all analytes. Relative recoveries varied from 62 to 117%, intra-day precision from 0.3 to 18.3% and inter-day precision from 1.3 to 20.8%. The proposed method was successfully applied to three samples of leached extracts of residues provided by the petrochemical oil industry. The composers phenanthranene (5.6 ng mL−1 ± 8.8%) in leachate extract 1 and anthracene (6.1 ng mL−1 ± 4.8%) in leachate extract 2 were quantified. Leachate extract 3 did not present quantifiable analytes by the proposed method. The results of this approach can provide a simple, easy to prepare and economic strategy (in terms of solvent and sample consumption) for the determination of PAH in aqueous samples.