Existing processes for the decontamination of heavy metals from water are found to be cost-prohibitive and energy-intensive which is totally against the sustainable concept of development. Green nanotechnology for water purification for ecosystem management, agricultural and industry is an emerging as leading global priority and occupies better position over the current state of water purification. Herein, the diafunctionalised polyaniline modified nanocellulose composite sorbent (PANI-NCC) has been used to introduce amine and imine functionalities for the removal of trivalent and hexavalent chromium from water bodies. The fabricated nanobiomaterial has been authenticated by modern spectroscopic, microscopic techniques. The modified PANI-NCC is rod-like in shape, ~60 nm in size. The roughness and crystallinity index is also quantified and found to be 49.67 nm and 84.18%, respectively. The optimised experimental finding provides the efficient removal of trivalent [Cr(III)] (47.06 mg/g; 94.12%) and hexavalent [Cr(VI)] (48.92 mg/g; 97.84%) chromium from synthetic waste water. The fabricated nano biosorbent is deemed to be a potent biosorbent for technological development to remove the toxic metals in the real environmental water samples.