Catalytic　oxidation　is　one　of　the　effective　pathways　for　completely　eliminating　volatile　organic　compounds　(VOCs)　emitted　from　industrial　and　transportation　activities.　Meanwhile,　single-atom　catalysts　have　excellent　application　prospects　in　numerous　reactions　due　to　their　high　metal　atomic　utilization　efficiency.　In　this　work,　we　adopted　a　novel　strategy　to　prepare　an　active　Pd/Co　single-atom　catalyst　(i.e.,　Pd1Co1/Al2O3)　for　benzene　oxidation.　The　successful　formation　of　the　atomically　dispersed　palladium　and　cobalt　species　on　Al2O3　was　verified　by　the　aberration-corrected　high-angle　annular　dark-field　scanning　transmission　electron　microscopy　and　X-ray　absorption　fine　structure.　By　the　in　situ　temperature-programmed　techniques　and　in　situ　diffuse　reflectance　Fourier　transform　infrared　spectroscopy,　we　observed　a　double　effect　of　the　palladium　and　cobalt　oxide　active　sites,　resulting　in　an　enhanced　performance　for　benzene　oxidation.　A　benzene　conversion　of　90　%　was　achieved　over　the　Pd1Co1/Al2O3　catalyst　at　250　degrees　C　and　a　space　velocity　of　40,000　mL/(g　h).　Interestingly,　the　catalyst　also　possessed　enhanced　sulfur　resistance　performance.　The　good　regeneration　ability　of　the　active　sites　in　the　catalyst　was　due　to　the　single-atom　dispersion　of　Pd　and　Co.　In　addition,　we　deduce　that　benzene　oxidation　might　occur　over　Pd1Co1/Al2O3　via　a　pathway　of　benzene　-＞　cyclohexadiene　-＞　phenol　-＞　quinone　-＞　maleate　-＞　acetate　-＞　CO2　and　H2O.　We　believe　that　the　obtained　results　can　provide　a　useful　idea　for　rationally　designing　the　double　active　site　single-atom　catalysts　and　understanding　the　mechanism　of　VOCs　oxidation.