Municipal solid waste landfills are one of the major sources of odor complaints. The determination of volatile compounds (VCs) emissions and their rates is a necessary prerequisite to calculate and study VCs dispersion and control. In this study a wind tunnel system has been introduced to investigate the VCs emission rates from the working face of a large anaerobic landfill in China. The VCs in gas samples were characterized by gas-chromatograph–mass-spectrometer. The emission rates of VCs increased linearly with sweeping velocity (0.1 m·s−1 to 0.5 m·s−1), and 0.28 m·s−1 was selected as the recommended practical operation sweeping velocity. The VCs emission rates on the working face at the landfill site were investigated during the course of a day. 31 chemical species divided into six chemical groups were quantified with the following emission rates: oxygenated compounds: 205.73–750.00 μg·m−2·s−1, hydrocarbons: 61.82–220.37 μg·m−2·s−1, aromatics: 15.55–40.11 μg·m−2·s−1, halogenated compounds: 11.71–31.57 μg·m−2·s−1, terpenes: 2.71–18.70 μg·m−2·s−1, and sulfur compounds: 1.29–10.84 μg·m−2·s−1. The highest average emission rates of VCs were found from midnight to dawn (1:00–7:00). These results provide key input parameters to users of VCs dispersion models to calculate buffer distances.