We developed an innovative approach that couples headspace solid-phase microextraction (SPME) with surface-enhanced Raman spectroscopy (SERS) to detect a volatile pesticide (i.e., fonofos) in a liquid complex matrix (i.e., apple juice). A gold nanoparticles-coated fiber was fabricated by reducing gold(III) on a chemically etched stainless steel wire to extract pesticide, using SPME. The fabricated fibers were then tested by a headspace-SPME method and a dip-SPME method, followed by SERS detection of fonofos in water and apple juice samples. Using the headspace-SPME method, we can detect as low as 5 ppb of fonofos in water and apple juice, compared with the dip-SPME method, which cannot detect lower than 10 ppb in water and 50 ppb in apple juice. This study demonstrated the potential capability of the headspace-SPME-SERS method for rapid (within 30 min) and sensitive detection of volatile and vaporizable compounds in complex matrices. The developed method could be a potential alternative approach to the gas chromatography method. Future work is needed to optimize the fiber by minimizing signal variation, and it should be tested in a variety of targeted compounds and matrices.