Two-dimensional nanomaterials decorated by metal nanoparticles have gained great interest, due to their potential applications in different areas ranging from electrochemical sensing to photothermal therapy. However, metal nanoparticles that are noncovalently immobilized on the surface of two-dimensional nanomaterials can be dissociated from their surface in the complex mediums. This challenge can be overcome by covalent attachment of nanoparticles to the surface of these platforms. In this work, MoS2 sheets are decorated by silver nanoparticles (AgNPs) through a reversible addition–fragmentation chain transfer (RAFT) reaction. Reactive centers were created on the surface of freshly exfoliated MoS2 and a two-dimensional platform with the ability of initiating the RAFT reaction was obtained. Afterwards, silver nanoparticles with acrylamide functionality were synthesized and attached on the surface of MoS2 sheets by the RAFT reaction. MoS2-AgNPs hybrids were characterized by different spectroscopy and microscopy methods as well as thermal and elemental analyses, and then they were used for the electrochemical determination of dipyridamole in aqueous solution. Taking advantage of the straightforward synthesis and the possible MoS2-AgNPs distance adjustment, a variety of hybrid systems with unique physicochemical and optoelectronic properties can be constructed by using this method.