A green, fast and selective approach for the synthesis of mono-substituted closo-decaborate derivatives [2-B10H9COR]2− has been established via a nucleophilic addition reaction between the carbonyl derivative of closo-decaborate [2-B10H9CO]− and the corresponding Grignard reagent RMgX, where R is the ethyl, iso-propyl, pentyl, allyl, vinyl and propynyl groups. This approach is accomplished under mild conditions with 70–80% yields. The significance of these derivative is their ability to constitute building blocks for polymeric integration via the allyl, vinyl and propynyl substituents. All products were characterized by 11B, 1H and 13C NMR, elemental analysis and mass spectrometry.