Gnaphalium affine D. Don, a medicinal and edible plant, has been used to treat gout in traditional Chinese medicine and popularly consumed in China for a long time. A detailed phytochemical investigation on the aerial part of G. affine led to the isolation of two new esters of caffeoylquinic acid named (−) ethyl 1, 4-di- O-caffeoylquinate ( 1) and (−) methyl 1, 4-di- O-caffeoylquinate ( 2), together with 35 known compounds ( 3– 37). Their structures were elucidated by spectroscopic data and first-order multiplet analysis. All the isolated compounds were tested for their xanthine oxidase inhibitory activity with an in vitro enzyme inhibitory screening assay. Among the tested compounds, 1 (IC 50 11.94 μmol·L –1) and 2 (IC 50 15.04 μmol·L –1) showed a good inhibitory activity. The current results supported the medical use of the plant.