Adsorbent is one of the most important factors for separation efficiency in fixed-bed purification techniques. The adsorption behavior of catechins and caffeine onto polyvinylpolypyrrolidone (PVPP) was investigated by static adsorption tests. The results showed that catechins rather than caffeine were preferred to adsorb onto PVPP since the adsorption selectivity coefficient of total catechins vs caffeine was around 22.5, and that adsorption of catechins could be described by the pseudo-second-order model. Adsorption amount of caffeine onto PVPP in green tea extracts solution was much higher than that in purified caffeine solution although the initial concentration of caffeine was similar in the two solutions, indicating the caffeine might be attached with catechins which were adsorbed by PVPP instead of being adsorbed by PVPP directly. The results also showed that the adsorption capacity of catechins and caffeine decreased with an increase in temperature, and that Freundlich and Langmuir models were both suitable for describing the isothermal adsorption of catechins, but not suitable for caffeine. The predicted maximum monolayer adsorption capacity of total catechins by PVPP was 671.77 mg g(-1) at 20 °C, which was significantly higher than that by other reported adsorbents. The thermodynamics analyses indicated that the adsorption of catechins onto PVPP was a spontaneous and exothermic physisorption process, revealing lower temperature was favorable for the adsorption of catechins. Elution tests showed that the desorption rates of catechins and caffeine were higher than 91% and 99% after two elution stages; in detail, almost all of the caffeine could be washed down at the water eluting stage, while catechins could be recovered at the dimethyl sulfoxide/ethanol solution eluting stage. Thus, the PVPP could be used as an excellent alternative adsorbent candidate for separating catechins from crude tea extracts, although some investigations, such as exploring the new eluants with low boiling point and high desorption efficiency, should be conducted furthermore.