A chemical modification of cotton fabrics by 2-diethylaminoethyl chloride (DEAE-Cl) was achieved, and the resulted cotton fabrics demonstrated salt-free dyeing properties with anionic dyes. Nucleophilic property of hydroxyl groups in cotton cellulose was enhanced under alkaline conditions and could react with DEAE-Cl, a chemical possessing both nucleophilic and electrophilic sites. The monolayered DEAE-grafted cotton cellulose could further react with DEAE-Cl to form multiple cationic quaternary ammonium salts (denoted as DEAE@Cotton), which are highly interactive with anionic dye molecules. The strong electrostatic interactions between the DEAE@Cotton and the dyes eliminated the use of inorganic salts in cotton dyeing process. The chemical structure and property of DEAE@Cotton were characterized and compared with untreated cotton. The DEAE@Cotton can be dyed in a salt-free system, and the dye exhaustion was faster than the conventional dyeing method due to the robust electrostatic interactions of the fabrics with anionic dyes. The dyed fabrics demonstrated outstanding color fastness under repeated washing, light exposure, and crocking. The dye adsorption process on DEAE@Cotton follows Langmuir isotherm model (R2 = 0.9667). The mechanism of enhanced dyeability was experimentally proved by treating the fabric with other anionic dyes in a salt-free system, proving the process to be environmentally friendly and cost-effective. Graphic abstract