great attention as alternatives to LIBs, in order to provide new opportunities for the substantial improvement of energy storage systems. [5][6][7][8][9][10][11][12] The alkali metals (Li, Na, and K) are located at the first group in the periodic table, possessing similar physicochemical properties. However, it is generally accepted that the larger cation radius of Na + (1.02 Å) and K + (1.33 Å) causes the sluggish diffusion kinetics, thus limiting the development of SIBs and PIBs. [6] Compared to the mature technology of LIBs, the developments of SIBs and PIBs are still at an initial stage.The common electrode materials in LIBs are generally not applicable to SIBs and PIBs. [13][14][15][16][17][18] Advanced electrode materials that can store large-sized Na + and K + are urgently desired. 2D layered transition metal dichalcogenides (TMDs), which are fundamentally and technically interesting, have been widely researched in energy storage field. [19][20][21] Vanadium disulfide (VS 2 ) is a typical family member of TMDs, which has attracted wide attention due to its layered structure with a large interlayer spacing of 0.57 nm together with excellent electric conductivity and weak van der Waals interlayer interaction. [22,23] The unique structure and properties of VS 2 make it an ideal host for the insertion/extraction of alkali metalions. Recently, the literature regarding the potential of VS 2 as an electrode for alkali metal-ion (Li + , Na + , and K + ) batteries with outstanding performance has been reported. [24][25][26][27][28][29] However, less attention has been paid to the relationship between the electrochemical performance and the storage mechanism in alkali metal-ion batteries. Revealing the detailed energy storage mechanisms, including the structural evolution, phase transition reactions, and ion diffusion kinetics, is highly significant for a deeper understanding of the electrochemistry about VS 2 and further optimization of its electrochemical performance in alkali metal-ion batteries.In this work, we systematically revealed and compared the electrochemical behaviors of the layered VS 2 cathode in three battery systems (LIBs, SIBs, and PIBs), including electrochemical performance, detailed structural evolution, and reaction kinetics during the alkali metal-ions insertion/extraction. In situ X-ray diffraction (XRD), ex situ transmission electron microscope (TEM), together with density functional theory (DFT) analysis were employed to accurately track the structural evolution of VS 2 during the discharging/charging processes, VS 2 is one of the attractive layered cathodes for alkali metal-ion batteries. However, the understanding of the detailed reaction processes and energy storage mechanism is still inadequate. Herein, the Li + /Na + /K + insertion/ extraction mechanisms of VS 2 cathode are elucidated on the basis of experimental analyses and theoretical simulations. It is found that the insertion/ extraction behavior of Li + is partially irreversible, while the insertion/extraction behavior of Na + /K...