Exploring the chemical reactivity of different atomic sites on crystal surface and controlling their exposures are important for catalysis and renewable energy storage. Here, we use two-dimensional (2D) layered molybdenum disulfide (MoS2) to demonstrate the electrochemical selectivity of edge versus terrace sites for Li-S batteries and hydrogen evolution reaction (HER). Lithium sulfide (Li2S) nanoparticles decorates along the edges of the MoS2 nanosheet versus terrace, confirming the strong binding energies between Li2S and the edge sites and guiding the improved electrode design for Li-S batteries. We also provided clear comparison of HER activity between edge and terrace sites of MoS2 beyond the previous theoretical prediction and experimental proof.