In this study, the polyethyleneimine (PEI) was grafted onto the biochars from chestnut shells and nori via the cross-linking reaction. Scanning electron microscopy, transmission electron microscopy and Fourier transferred infrared spectroscopy analysis indicated that the PEI was successfully grafted on the surface of biochars. The PEI modified and pristine biochars were used as adsorbents to remove Cr(VI) from aqueous solutions as a function of pH, ionic strength, contact time and initial concentrations of Cr(VI) through batch technique. The strongly pH-dependent and ionic strength-independent of Cr(VI) sorption indicated that the sorption was mainly dominated by electrostatic interaction and inner-sphere surface complexation. The maximum sorption capacities of PEI modified chestnut shell and nori biochars were 141.42 and 222.84 mg/g, respectively, which were significantly higher than those of pristine biochars. The PEI grafted onto the biochars significantly enhanced Cr(VI) sorption capacity because PEI, which contains volumes of amine/imine groups, provided an excellent platform for Cr(VI) ions removal. In addition, the sorption–desorption experimental results indicated that the PEI modified biochars possessed a stable and recyclable performance. All these results manifested that the PEI modified biochars could be applied as environmentally friendly and efficient adsorbents for the removal of Cr(VI) from wastewater.