Formation Of SiO2-B2O3 gel fibers and oxides was investigated by the sol-gel method using tetraacetoxysilane (TAS) and boron tri-n-butoxide (BTB), Low molecular weight borosiloxanes (BS) were formed by the reaction of TAS with BTB in THF. Partial alkoxylation and hydrolysis of BS followed by further condensation of the resulting polymer (PBS) solutions led to the formation of highly polymerized polyborosiloxanes (HPBS) with good spinnability. Gel fibers were obtained by dry spinning of HPBS. The compositions of PBS and gels were not consistent with that in feed. Heat treatment of the gels, however, provided SiO2-B2O3 oxides with compositions almost compatible with those of the gels.