In this study, an efficient route to synthesizing polyethyleneimine-modified ultrasonic-assisted acid hydrochar (PEI-USAH) is developed and reported. Ultrasonic irradiation technique was used as surface modification method to shorten the crosslinking reaction for hydrochar and polyethyleneimine (PEI). The PEI-USAH showed an excellent adsorption capacity for Cr(VI) from aqueous solution. The physicochemical properties of this PEI-modified adsorbent were comparatively characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller analysis and CNHS analysis. The effects of contact time, initial pH, and biosorbent dose on adsorption capacities were investigated. The batch adsorption experiments showed that PEI-USAH possessed the maximum adsorption capacities of 94.38 mg/g and 330.84 mg/g for initial Cr(VI) concentration of 100 mg/L and 500 mg/L, respectively. Furthermore, this adsorption process could be fitted to Langmuir adsorption and described by the pseudo second order kinetic model. Based on the above findings, PEI-USAH could be used as a potential adsorbent for removal of Cr(VI) from wastewater.