Removal of cerium from environmental and aqueous streams is essential in waste water rejuvenation processes. Nitrogen modified graphene nano walls (N-GNWs) have shown ultra-high sorption efficiency of trivalent cerium from aqueous medium (Kd > 2 × 107) and a large sorption capacity of ∼ 2500 mg/g is achieved. N-GNWs were deposited on carbon paper substrate using PECVD technique. The three-dimensional nature of N-GNWs are revealed from high resolution FESEM images. Raman spectroscopic studies have shown that GNWs are defective and possess a few layer graphene like structure. Secondary Ion Mass Spectroscopic studies of the Ce sorbed N-GNWs and optical emission spectroscopy of the residual solution confirm the sorptive retrieval of cerium. Visual Minteq based ionization model is introduced to explain high (>90 %) sorption of Ce at pH≥7 and the mechanistic aspects of sorption for standard Cerium solution is discussed. The sorption involves attachment of cerium hydroxyl ions to the active cites on the sorbent surface.