With the significant obstacles that have been conquered in lithium-sulfur (Li-S) batteries, it is urgent to impel accelerating development of room-temperature Li-S batteries with high energy density and long-term stability. In view of the unique solid-liquid-solid conversion processes of Li-S batteries, however, designing effective strategies to address the insulativity and volume effect of cathode, shuttle of soluble polysulfides, and/or safety hazard of Li metal anode has been challenging. An atomic layer deposition (ALD) is a representative thin film technology with exceptional capabilities in developing atomic-precisely conformal films. It has been demonstrated to be a promise strategy of solving emerging issues in advanced electrical energy storage (EES) devices via the surface modification and/or the fabrication of complex nanostructured materials. In this review, the recent developments and significances on how ALD improves the performance of Li-S batteries were discussed in detail. Significant attention mainly focused on the various strategies with the use of ALD to refine the electrochemical interfaces and cell configurations. Furthermore, the novel opportunities and perspective associated with ALD for future research directions were summarized. This review may boost the development and application of advanced Li-S batteries using ALD.