Cotton modification exhibited great potential in the fabric dyeing industry. A bifunctional cationic polymer with a moderate cationic degree and low molecular weight was achieved via free radical polymerization between dimethyl diallyl ammonium chloride and allyl glycidyl ether. Then, it was further utilized for the modification of cotton fabrics. The formation of the cationic polymer was identified using Fourier transform infrared and nuclear magnetic resonance spectroscopies. The structure and properties of both treated and untreated cotton were analyzed by X-ray photoelectron spectroscopy and scanning electron microscopy. The modified cotton fabrics could be salt-free dyed with reactive dyes at low temperatures. While obtaining satisfactory color fastness and leveling properties, the dyeability of the modified cotton was improved significantly compared with the conventional dyeing of native cotton. Besides, the prepared cationic polymer has good flocculating properties to avoid secondary pollution, suggesting high potential for achieving an economical and eco-friendly dyeing process.