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In the present paper, we report the successful preparation of high density, well‐defined polymer brushes by RAFT polymerization on silica nanoparticles. Our strategy includes (i) “grafting from” approach for brush formation, (ii) facile click reaction to immobilize RAFT agent, (iii) synthesis of R‐supported chain transfer agent (CTA) over Z‐supported CTA, and (iv) use of more active trithiocarbonate RAFT agent over conventional dithioester type RAFT agent. With the advantage of the properties of high‐density polymer brushes, these diblock copolymer‐modified silica nanoparticles open the route to the elaboration of a new family of nanocomposite colloids with potential applications in responsive or smart systems.