Abstract: The best resin was selected from nine kinds of macroporous resins by adsorption and resolution rate as indicators.Pinus sylvestris L.barks polyphenol was secondary purified with the best resin using purity and recovery rate as index.Finally, the composition of secondary purified polyphenol was preliminary analyzed with HPLC-DAD- ESI-MS method. The results showed that the macroporous resin X- 5 was the best resin and 60% ethanol was suitable for eluent. The optimum condition of secondary purification was that sample solution concentration was 4.0mg /mL, chromatographic column diameter hight ratio was 1 ∶ 30, sample solution volume was 60mL, eluting speed was 2BV/h.Under this condition, the purity of Pinus sylvestris L.barks polyphenol increased from 62.06% ± 1.67% to 72.99% ± 0.98%, the recovery rate was 87.26% ± 2.42%. The main composition of secondary purification product were: procyanidins trimer, procyanidin dimmer type B2, 5-galloylquinic acid, epicatechin and ellagic acid.