Cellulose, a kind of polymer containing abundant functional groups, has widespread use in the adsorptive removal of environmental pollutants. An efficient and environmental friendly polypyrrole (PPy) coating approach is employed to modify the agricultural by-product straw derived cellulose nanocrystal (CNC) into excellent property adsorbents for removing the heavy metal ion of Hg(II). The FT-IR and SEM-EDS results demonstrated that PPy is formed on the surface of CNC. Consequently, the adsorption measurements proved that the obtained PPy-modified CNC (CNC@PPy) possesses a remarkably enhanced Hg(II) adsorption capacity of 1095 mg g−1, owing to a plentiful functional group of doped Cl element on the surface of CNC@PPy by forming Hg2Cl2precipitate. The results of the study suggest that the Freundlich model is more effective than the Langmuir model at describing the isotherms, while the pseudo-second order kinetic model is better suited to correlating with the experimental data compared to the pseudo-first order model. Further, the CNC@PPy exhibits an outstanding reusability, capable of maintaining 82.3% of its original Hg(II) adsorption capacity after five successive adsorption cycles. The findings of this work reveal a method to convert the agricultural by-product into high performance environmental remediation materials.