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Defects in transition metal dichalcogenides play important roles in the field of the catalytic hydrogen evolution reaction (HER). However, the use of defective MoS2 as HER catalysts remains controversial because the types of defects are various, including zero-dimensional point defects, one-dimensional linear defects, and two-dimensional plane defects. Recently, novel structures of linear defects have drawn more and more attention, and it is necessary to explore their unique properties. This review focuses on the formation mechanism, fabrication method, accurate atomic structure, and catalytic hydrogen evolution mechanism of sulfur line vacancies in MoS2 as electrocatalysts. The structure–activity relationship between line defects and catalytic performance is discussed in detail. This will provide a route for the design of excellent catalysts by engineering line defects.