Novel silylated hydroborate clusters comprising the closo-decaborate cage were prepared and characterized by ¹H, ¹³C, ¹¹B, ²⁹Si NMR and mass spectroscopy ESI. The synthesis of such silylated clusters was achieved using reactive derivatives of [B₁₀H₁₀]²⁻, [1-B₁₀H₉N₂]⁻ and [2-B₁₀H₉CO]⁻. These silylated decaborate clusters constitute a new class of precursors that can be covalently anchored onto various silica supports without any prior surface modification. As a proof of concept, the synthesized precursors were successfully anchored on mesoporous silica, SBA-15 type, in different percentages, where the mesoporous material retained its structure. All materials modified with closo-decaborate were characterized by ¹¹B and ²⁹Si solid state NMR, XRD, TEM and nitrogen sorption.