Counter‐current chromatography is a chromatographic separation and purification technique being developed. The development of different elution modes has significantly contributed to this field. Multiple dual‐mode elution is a method developed based on dual‐mode elution, which consists of a series of changing cycles of the phase role and the direction by switching between normal and reverse elution modes of counter‐current chromatography. This dual‐mode elution method takes full advantage of the liquid nature of stationary and mobile phases of counter‐current chromatography and effectively improves the separation efficiency. So, this unique elution mode has gained extensive attention for separating complex samples. This review mainly describes and summarizes in detail its development, applications, and characteristics in recent years. Meanwhile, its advantages, limitations, and future outlook also have been discussed in this paper.