Controlled and straightforward functionalization are relevant strategies to obtain MoS2 platforms with defined functionality and improved processability. In this work, an efficient strategy for the functionalization of MoS2 using Reversible Addition Fragmentation Transfer (RAFT) polymerization is reported. The RAFT reagent was directly created on the surface of freshly exfoliated MoS2 and the obtained two-dimensional platform was used for the polymerization of styrene and acrylamide monomers. Various ratios of divinylbenzene were used to crosslink polystyrene brushes and create a polymeric coverage on the surface of MoS2. Furthermore, the polymerization of a mixture of styrene and acrylamide monomers using a MoS2-based RAFT agent resulted in two-dimensional platforms containing copolymer brushes. The structures of the synthesized two-dimensional materials were investigated using different spectroscopy and microscopy techniques as well as thermal and elemental analyses. This research provides an efficient method for the preparation of functional two-dimensional MoS2 nanostructures using RAFT polymerization in gram scale.