Organic dye pollution in the water environment is a problem of global concern. Adsorption is demonstrated as a promising technology to remove organic dyes from wastewater, in which the development of highly-efficient adsorbents is still the challenging task. Herein, we reported the facile fabrication of polyamine-based cyclophosphazene hybrid (PCP-NH2) hollow microcapsules with cross-linked structure, generated by one-step precipitation polymerization between hexachlorocyclotriphosphazene and branched polyethyleneimine, and subsequent acetone treatment. Their morphology, composition and structure were confirmed by SEM, TEM, FTIR, TGA, and XPS. The endowment of hollow PCP-NH2 microcapsules as potential adsorbents were thoroughly evaluated using eight organic dyes with different surface charges. The adsorption action of hollow PCP-NH2 microcapsules highly depends on the surfaces charges, exhibiting highly-efficient and selective adsorption behavior towards anionic dyes. Especially, The adsorption capacity of the hollow PCP-NH 2 microcapsules towards anionic dyes of EY, ACBK, MO and EB reaches up to 1196.36, 1190.65, 1142.77 and 1040.92 mg/g at 25 degrees C, respectively. The adsorption kinetics shows a better fit to pseudo second-order kinetic model, compared to pseudo-first-order kinetic and Weber's intraparticle diffusion models. The adsorption equilibrium data followed the Langmuir isotherm well. The adsorption thermodynamic experiments demonstrated that adsorption was a physisorption process with endothermic and spontaneous characteristic. (C) 2019 Elsevier Inc. All rights reserved.