In the present work, leucoemeraldine-based hybrid porous polyanilines (LHPPs) have been synthesized by the Friedel-Crafts reaction of leucoemeraldine and octavinylsilsesquioxane (OVS) for Cr(vi) removal. The resulting LHPPs were characterized by Fourier transform infrared spectroscopy, powder X-ray diffraction, thermogravimetric analysis, scanning electron microscopy and N2 adsorption-desorption. The findings indiated that the LHPPs were amorphous, with apparent surface areas (S BET) in the range of 147 to 388 m2 g-1 and total volumes in the range of 0.13 to 0.44 cm3 g-1. Cr(vi) removal experiments displayed that the LHPPs exhibited highly efficient Cr(vi) removal performance. The maximum Cr(vi) removal capacity of LHPP-1 was 990.1 mg g-1 at 308 K and pH 1, which is higher than those of other reported polyaniline-based adsorbents. The adsorption process was a spontaneous, endothermic and chemical adsorption process. The adsorption behavior agreed well with Langmuir models and pseudo second-order equations. X-ray photoelectron spectroscopy and Fourier transformed infrared (FTIR) spectroscopy analysis revealed that the highly efficient Cr(vi) removal performance can be mainly attributed to the existence of numerous amine and imine groups on the surface of the LHPPs; these can function as adsorption active sites for Cr(vi) removal through electrostatic adsorption and reduction to Cr(iii) under acidic conditions. Moreover, the LHPPs exhibited excellent adsorption selectivity for Cr(vi) despite the presence of other metal ions (K+, Cu2+, Mn2+) and anions (NO3 -, SO4 2-). Therefore, the LHPPs have potential applications for Cr(vi) removal in industrial wastewater.