Polycondensation of boric acid and vinyltriethoxysilane in 1:2, 1:1.5 and 1:1 mole ratio in diglyme at 83–87 °C for 3 h using hydrochloric acid as catalyst afforded vinylfunctionalized borosiloxane oligomers soluble in the reaction medium. Complete removal of ethanol, the by-product, and diglyme rendered the oligomers intractable due to the advancement of polycondensation. They were characterized by FTIR and TGA and converted to ceramics by heat treatment at 900 °C, 1500 °C and 1650 °C in argon atmosphere. The ceramics obtained were characterized by IR, Raman, 13C-and 29Si-solid state NMR spectroscopy and XRD. These studies infer the formation of SiOC/SiBOC glass on pyrolysis of these oligomers at 900 °C and onset of formation of β-SiC at 1500 °C. On further heat treatment at 1650 °C, complete conversion of the ceramic to a mixture of α and β-SiC was observed along with the presence of diamond like carbon phases.