A solvent-free and simple method based on headspace solid-phase microextraction (HS-SPME) was developed in order to determine simultaneously 36 common pesticides and breakdown products (mostly pyrethroids and organochlorine compounds) in soil. The analysis was carried out by gas chromatography with micro-electron-capture detection (GC-μECD). As far as we know, this is the first study about the SPME of pyrethroid insecticides from soil. Factors such as extraction temperature, matrix modification by addition of water, salt addition (% NaCl) and fiber coating were considered in the optimization of the HS-SPME. To this end, a 3×2³⁻¹ fractional factorial design was performed. The results showed that temperature and fiber coating were the most significant variables affecting extraction efficiency. A suitable sensitivity for all investigated compounds was achieved at 100°C by extracting soil samples wetted with 0.5mL of ultrapure water (0% NaCl) employing a polyacrylate (PA) coating fiber. Using the recommended extraction conditions with GC-μECD, a linear calibration could be achieved over a range of two orders of magnitude for both groups of analytes. Limits of detection (LODS) at the sub-ngg⁻¹ level were attained and relative standard deviations (RSDs) were found to be lower than 14% for both groups of pesticides. Matrix effects were investigated by the analysis of different soil samples fortified with the target compounds. The method accuracy was assessed and good recovery values (>70%, in most cases) were obtained. The method was also validated with a certified reference material (RTC-CRM818-050), which was quantified using a standard addition protocol. Finally, the proposed HS-SPME-GC-μECD methodology was further applied to the screening of environmental soil samples for the presence of the target pesticides.