Lignin-carbohydrate complexes (LCC) have shown great potential as biocompatible antioxidants. But it is difficult to isolate LCC efficiently from lignocellulose by traditional Solid-Liquid Extraction method (SLE), which is blamed to the innate bioimpedance caused by the complex supramolecular structure of the lignocellulose, and a great mass transferring resistance between the extracting solution and solid lignocellulose. To release these restrictions above and improve the efficiency of LCC isolation, a modified isolating method named Liquid-Liquid Extraction (LLE) was proposed, in which ball-milled wheat stalk was dissolved in lithium chloride/dimethyl sulfoxide (LiCl/DMSO) solution, then regenerated by dioxane aqueous to extract LL-LCCs. The effect of the LLE on the LCC isolating was evaluated and results showed that both the total yield and antioxidant activity of LL-LCCs were higher than that of control group. It proved the dissolution of wheat stalk in LiCl/DMSO solution could reduce the mass transfer resistance during the extraction. Due to the catalyzation of LiCl as Lewis acid, LL-LCCs had lower molecular weight but more phenolic hydroxyl groups and higher S/G ratios. These factors of LL-LCCs resulted in greater free-radical scavenging ability than control sample. The modified isolation protocol could facilitate the isolation and utilization of LCCs as a free-radical scavenger.