In this study, facile fabrication of three-dimensional (3D) pompon-like gold/zinc oxide (Au/ZnO) porous microspheres by hydrothermal procedure was investigated. These microspheres were utilized as solid phase microextraction (SPME) coating for determination of volatile fatty acids (VFAs) from foot odor coupling with gas chromatography-mass spectrometry (GC-MS). SEM and TEM characterizations showed that as-prepared material was composed of 1D porous nanowires and presented a uniform coating on stainless-steel wire. The extraction of VFAs including propanoic acid, butyric acid, isobutanoic acid, isovaleric acid, hexanoic acid, and heptylic acid was carried out by headspace model after sampling from human foot using cotton wool strips. Following optimization of extraction parameters including extraction temperature and time and desorption temperature and time, the as-prepared SPME coating presented better extraction efficiency than commercial DVB/CAR/PDMS fiber towards all the VFAs due to its excellent properties. Under the optimized conditions, the method exhibited good linearity (0.5-200 ng) with regression coefficients (R) ranging from 0.9836 to 0.9981 for all the analytes. The limits of detection ranged from 0.017 to 0.098 ng. Single fiber repeatability varied from 6.5% to 11.2% and the fiber-to-fiber reproducibility ranged from 8.6% to 12.3%. The proposed method was successfully applied for extraction and determination of VFAs from foot odor after sampling using cotton wool strips.