Noble metal nanoparticle decoration is a representative strategy to enhance selectivity for fabricating chemical sensor arrays based on the 2-dimensional (2D) semiconductor material, represented by molybdenum disulfide (MoS2). However, the mechanism of selectivity tuning by noble metal decoration on 2D materials has not been fully elucidated. Here, we successfully decorated noble metal nanoparticles on MoS2 flakes by the solution process without using reducing agents. The MoS2 flakes showed drastic selectivity changes after surface decoration and distinguished ammonia, hydrogen, and ethanol gases clearly, which were not observed in general 3D metal oxide nanostructures. The role of noble metal nanoparticle decoration on the selectivity change is investigated by first-principles density functional theory (DFT) calculations. While the H2 sensitivity shows a similar tendency with the calculated binding energy, that of NH3 is strongly related to the binding site deactivation due to preferred noble metal particle decoration at the MoS2 edge. This finding is a specific phenomenon which originates from the distinguished structure of the 2D material, with highly active edge sites. We believe that our study will provide the fundamental comprehension for the strategy to devise the highly efficient sensor array based on 2D materials.