An efficient preparative separation and enrichment process of polyphenols from sunflower kernel extracted by acid solution has been developed in the present study. 3-O-caffeoylquinic acid (CQA), 4-O-CQA and 5-O-CQA were identified as the main polyphenols in crude extract. The adsorption capacity and desorption ratio for total polyphenols of nine macroporous resins had been evaluated and XDA-1 resin was found to be the most suitable resin for the separation of polyphenols. It was found that ultrafiltration as preliminary treatment could improve the purity of crude extract from 4% to 15%. After that, the extract was submitted to XDA-1 resin column. The optimized purification conditions were obtained as following: polyphenol concentration in sample solution of 2.0 mg/mL, sample pH of 3.0, flow rate of 2 bed volume (BV)/h, sample volume of 30 BV. When the adsorption is done, 10% (V/V) ethanol was applied to the column to wipe off the impurity at 4 BV/h. Then polyphenols were eluted with 50% (V/V) ethanol at 4 BV/h. With the enrichment on XDA-1 resin, the purity of polyphenol in the final product was increased from 15% to 77%, and recovery yield of 82.3% was obtained. Therefore, combination of ultrafiltration and macroporous resin separation provided an efficient and cost-effective method for recovery of CQAs from sunflower kernel extract.