A facile freeze-drying method was presented to fabricate three dimensional (3D) honeycomb-like structured nanoscale zero-valent iron/chitosan composite foams (ICCFs) for effective removal of inorganic arsenic in water. It was found that freezing temperature has important influence on the formation of 3D network structure of ICCFs. The ICCFs obtained at freeze temperature of -80 degrees C exhibits oriented porous structure with good mechanical property than that at -20 degrees C, thus improved excellent removal capability of As(III) and As(V) up to 114.9 mg g(-1) and 86.87 mg g(-1), respectively. Further, the adsorption kinetics of ICCFs on As(III) and As(V) can be described by pseudo-second order model and their adsorption isotherms follow Langmuir adsorption model. The superior removal performance of ICCFs on As(III) and As(V) can be ascribed to its oriented porous structure with abundant adsorption active sites resulted from nZVI and O, N-containing functional groups in ICCFs. Importantly, it was found that the O, N-containing functional groups of chitosan in ICCFs can adequately bind with the dissolved Fe3+ ions from oxidation of nZVI to form Fe3+-Chitosan complex during removal of As(III) and As(V), thus effectively avoiding the dissolved Fe3+ ions into solution to produce secondary pollution. A possible adsorption-coupled reduction mechanism of ICCFs on As(III) and As(V) was also proposed based on the experimental results. We believe that this work would be helpful to develop low-cost and abundant chitosan-based materials as high performance adsorbents for environmental remediation applications. (C) 2016 Elsevier Inc. All rights reserved.