In this study, 5,17-bis-[(4-benzylpiperidine)methyl]-25,26,27,28-tetrahydroxy-calix[4]arene (3) has been prepared by the treatment of calix[4]arene with a secondary amine (4- benzylpiperidine) and formaldehyde by means of Mannich reaction. The prepared Mannich base (3) has been grafted onto [3-(2,3-epoxypropoxy)-propyl]-trimethoxysilanemodified Fe3O4 magnetite nanoparticles (EPPTMS-MN) in order to obtain 5,17-bis-[(4- benzylpiperidine)methyl]-25,26,27,28-tetrahydroxy calix[4]arene-grafted EPPTMS-MN (BP-calix[4]arene-grafted Fe3O4). All new compoundswere characterized by a combination of FTIR and 1H-NMR analyses. The morphology of the magnetic nanoparticles was examined by transmission electron microscopy. Moreover, the studies regarding the removal of arsenate and dichromate ions from the aqueous solutions were also carried out by using 5,17-bis-[(4-benzylpiperidine)methyl] 25,26,27,28-tetrahydroxy-calix[4]arene in liquid liquid extraction and BP-calix[4]arene-grafted Fe3O4 (4) in solid liquid extraction experiments. The extraction results indicated that 3 is protonated at proton-switchable binding sites in acidic conditions. Hence, facilitating binding of arsenate and dichromate is resulted from both electrostatic interactions and hydrogen bonding. To understand the selectivity of 3, the retention of dichromate anions in the presence of Cl-, NO3-, and SO42- anions at pH 1.5 was also examined. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.