Adsorption is an important technology for the separation of different tea components. The adsorption behavior of L-theanine onto adsorbents was comprehensively studied in this paper. Among tested adsorbents, cation exchange resin ZGSPC106Na and D001SD were suitable for separating L-theanine, PVPP and PA-6 for catechins and macroporous resin HPD-400 for caffeine. Adsorption of L-theanine onto the cation resins was significantly influenced by the acidity, contact time and temperature. The adsorption behavior could be described by the pseudo-second-order rate equation and fitted to Langmuir and Freundlich models. ZGSPC106Na exhibited higher adsorption capacity, while D001SD showed higher adsorption selectivity. These might be attributed to the distinctive structure of the two resins and different ionization of the adsorbates. A method for simultaneous preparation of decaffeinated polyphenols, caffeine-enriched extract and decaffeinated L-theanine was established through successive separation on the columns fulfilled with PA-6, HPD-400 and D001SD, respectively.