4-chloromethylphenylisocynate has been uniformly bounded to silanol functionalities of porous partially sub-2µm silica monolith particles via isocyanate-hydroxyl coupling reaction catalyzed by Dibutytindichloride which effectively controls the density of the Ligand-attachment. Sodium diethyldithiocarbamate was attached to halogen terminated Ligand as the initiator reagent, which initiates styrene mediated reversible addition fragmentation chain transfer (RAFT) polymerization. Sub-2μm silica monolith particles were synthesized by a delicately controlled process of sol-gel formation via a sophisticated multi-step heating procedure followed by easy grinding and calcination. This overall process results in the formation of thin, uniformly distributed polymer film on the entire surface of silica monolith particles which showed tremendously high separation efficiency with number of theoretical plates Ca.185, 000/m when used as chromatographic media. Chromatographic execution was carried out using a mobile phase of 60/40 ACN/water, containing 0.1% TFA, with a flow rate of 15µl/mint. This is the very first study to get tremendously high separation efficiency using porous monolith particulate stationary phase.