In this work, the use of the ionic liquid (IL) 1,3-dipentylimidazolium hexafluorophosphate ([PPIm][PF6]) as an alternative extractant for IL dispersive liquidliquid microextraction (IL-DLLME) of a group of pesticides and metabolites (2-aminobenzimidazole, carbendazim/benomyl, thiabendazole, fuberidazole, carbaryl, 1-naphthol, and triazophos) from soils is described. After performing an initial ultrasound-assisted extraction (USE), the IL-DLLME procedure was applied for the extraction of these organic analytes from soil extracts. Separation and quantification was achieved by high-performance liquid chromatography (HPLC) with fluorescence detection (FD). Calibration, precision, and accuracy of the described USE-IL-DLLME-HPLC-FD method using [PPIm][PF6] as an alternative extractant was evaluated with two soils of different physicochemical properties. Accuracy percentages were in the range 93118% with RSD values below 20%. A comparison of the performance of [PPIm][PF6] versus that of the so-common 1-hexyl-3-methylimidazolium hexafluorophosphate ([HMIm][PF6]) was accomplished. Results indicate a comparable extraction efficiency with both ILs, being slightly higher with [HMIm][PF6] for the metabolite 2-aminobenzimidazole, and slightly higher with [PPIm][PF6] for triazophos. In all cases, LODs were in the low ng/g range (0.0214.2 ng/g for [HMIm][PF6] and 0.0260.5 ng/g for [PPIm][PF6]). As a result, the current work constitutes a starting point for the use of the IL [PPIm][PF6] for further analytical approaches.