The traditional pre-treatment of cotton fabric hardly meets the requirement of low carbon emissions due to its large energy consumption and wastewater discharge. In this study, a low-temperature and near-neutral strategy was designed by establishing a tetraacetylethylenediamine (TAED)-activated sodium percarbonate (SPC) system. First, the effects of SPC concentration, temperature and duration on the whiteness index (WI) and capillary effect of cotton fabrics were investigated. Particularly, excess SPC’s ability to create an additional bleaching effect was studied. The optimized activated pre-treatment was compared with the traditional pre-treatment in terms of the bleaching effect and energy consumption. Further, the degradation of morin, which is one of the natural pigments in cotton, was carried out in a homogeneous TAED/SPC system to reveal the bleaching mechanism. Lastly, the application performance of the treated cotton was evaluated by characterizing the dyeability, mechanical properties, morphology, etc. The research results showed that temperature had a significant influence on both the WI and capillary effect, followed by the SPC concentration and duration. The WI was positively correlated with the SPC concentration, but excess SPC could not produce an obvious additional effect. The WI of the fabric increased by 67.6% after the optimized activated bleaching using 10 mmol/L SPC and 15 mmol/L TAED at 70 °C for 30 min. Compared with the traditional process performed at 95 °C for 45 min, the activated process produced approximately 39.3% energy savings. Research on the bleaching mechanism indicated that the reactive species that participated in degrading the morin were the hydroxyl radical and superoxide radical, and the contribution degree of the former was larger than that of the latter. Two degradation components with molecular weights of 180 and 154 were detected using mass spectroscopy. Based on this, the bleaching mechanism of the TAED/SPC system was proposed. Moreover, the fabric after the activated pre-treatment had a suitable dyeability and strength, a lower wax residual and a smoother and cleaner fiber surface. The encouraging results showed that TAED/SPC is a promising bleaching system that is conducive to the sustainable advance of the textile industry.