A simple and environmentally friendly methodology for headspace solid-phase microextraction (HS-SPME) using a new fiber coated with polydimethylsiloxane- poly(vinyl alcohol) (PDMS/PVA) is reported for the trace determination of organochlorine (OCP) and organophosphorus (OPP) pesticides in herbal infusions of Passiflora L. by GC-ECD. The capacity of the PDMS/PVA coating for the pesticides was compared to that of commercial PDMS fibers, with advantageous results. The effects of parameters such as the sample ionic strength, dilution of the infusion, extraction temperature and time were investigated. The optimized conditions for the determination of OCP and OPP in Passiflora L. infusions were extraction time and temperature, respectively, of 38 min and 67.5°C, with 5 min of sample/headspace equilibration time. The analytical curves for the range between 0.04 ng mL ^-1 to 6 ng mL ^-1 of each compound presented a good quality (correlation coefficients of 0.921 or better). The detection limits for the OCP and OPP in these matrices varied from 0.01 ng mL ^-1 (β-endosulfan) to 1.5 ng mL ^-1 (malathion). The sensitivity of studied methodology was adequate, as well as its accuracy (78.7-91.5%) and precision (R.S.D. = 1.2-14.2%).