Efficient removal of lead from aqueous media remains a serious task for public health and environment. Here polyacrylonitrile (PAN) monolith is fabricated by means of thermally induced phase separation (TIPS), a novel method that can be used for the preparation of hierarchically structured monolith without any templates assisted. Three hierarchically structured adorbents (D-PAN, H-PAN, A-PAN) based on PAN monolith were successfully prepared by reacting with diethylenetriamine (DETA), sodium hydroxide, and hydroxylamine hydrochloride, respectively. The Pb (II) adsorption ability of all modified samples was determined by a series of batch tests. Experimental data illustrated that all samples showed excellent Pb (II) adsorption ability and the maximum adsorption capacity of D-PAN, H-PAN, and A-PAN was 144 mg g(-1), 206 mg g(-1) and 242 mg g(-1), respectively. The feasible preparation of hierarchically monolithic adsorbents with high adsorption capacities opens a new expectation in the potential application for engineering. (C) 2016 Elsevier B.V. All rights reserved.