α-Fe2O3 nanoparticle has been widely used in water purification because of its effective adsorption performance. However, aggregation and difficulty in separation limit its practical application. Herein, we presented a polyacrylonitrile (PAN) nanofiber mat decorated with α-Fe2O3 as adsorbent for effective removal of Pb 2+ from contaminated water, which can solve the above problems easily. The α-Fe2O3/PAN nanofiber mats were prepared via electrospinning followed by a facile hydrothermal method and characterized by SEM, HRTEM, FTIR and XRD. We demonstrated the formation mechanism of α-Fe2O3 anchored on PAN nanofiber surface consists of the adsorption of iron ions on the surface of PAN, and then the α-Fe2O3 nucleation and growth. The pH value of FeCl3 solution has a great impact on the formation process of α-Fe2O3/PAN nanofiber mat, which lead to the variation of morphology and the quantity of the coating coverage. When the pH value was 2.4, polyhedral particles were coated on PAN nanofibers uniformly and the optimized α-Fe2O3/PAN nanofiber mat was obtained. Controlled experiments were carried out to quantify the adsorption capacities of different samples and adsorption kinetics. The isotherm data from our experiments fitted well to the Langmuir model and the adsorption process can be described using the pseudo-second-model. Finally, the adsorption mechanism for Pb 2+ was investigated and the results revealed that ion exchange between proton of surface hydroxyl groups and Pb 2+ was accounted for the adsorption. Fig. 6 The effect of contact time on Pb 2+ adsorption capacity with different initial concentration (a), SEM image of α-Fe2O3/PAN (S2.4) after adsorption (b), the fitting results using pseudo first order (c), and pseudo second order (d) kinetic model.