Ethyl acetate fraction (EAF) from Rhus verniciflua Stokes is an important source of bioactive compounds. The aim of this study was the tentative identification and quantification of phenolic compounds, comparison of the phenolic structure-antioxidant activity relationships. Twelve compounds of EAF belonging to polyphenol types were detected by high performance liquid chromatography and analysed on line with negative ion electrospray ionisation tandem mass spectrometry, which were ethoxy 3-hydroxy benzoic acid, gallic acid (GA), 3,4-dihydroxy amygdalic acid, gallic acid cetyl ester, protocatechuic acid (PA), fustin, ethyl gallate (EG), garbanzol, fisetin, sulfuretin, butin and 3,7-dihydroxyflavanone-4'-rhamnoside. The antioxidant activity were evaluated based on the different types of radical scavenging capacities, i.e. DPPH·, ABTS·+ and OH. The antioxidant capacity of EAF mainly depended on the GA, EG, PA, fisetin, sulfuretin and butin. The phenolics exhibited a dose-dependent behaviour and high antioxidant ability.