In this article, a serial of bi-functionalized hollow polymer particles (BF-HPPs), containing both carboxylate and different amide/amine groups [HPP-NH2, HPP-ethylenediamine (EDA), and HPP-diethylenetriamine (DETA)], were specially designed and synthesized to investigate the effect of neighboring amino groups on their adsorption/desorption behavior. Due to the high density of carboxylate groups, these BF-HPPs can serve as efficient adsorbents for selective removal of positively charged methylene blue (b-MB). With increasing chain length of the neighboring amino groups, the maximum adsorption capacities (q(max)) at pH 7 decrease dramatically from 606.1 mg g(-1) for HPP-NH2, to 404.9 mg g(-1) for HPP-EDA, and 332.2 mg g(-1) for HPP-DETA, due to increasing steric hindrance. Significantly, the equilibrium adsorption can be achieved within 15 min for HPP-EDA and HPP-DETA, while it takes more than 720 min for HPP-NH2. Moreover, the q(max) of HPP-DETA exhibits remarkable pH-sensitive property, which decreases sharply to 32.7 mg g(-1) at pH 3 due to strong electrostatic repulsion between positively charged ammonium groups and b-MB molecules. Accordingly, the desorption efficiency of HPP-DETA reached up to 94% after one desorption step, which is much higher than that of HPP-EDA (78%) and HPP-NH2 (60%). The absorbed b-MB can be facilely desorbed and the adsorption capacity of the regenerated HPP-DETA keeps above 95% after five consecutive adsorption-desorption cycles. (c) 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1404-1413