Branched higher silicon hydrides SinH2n+2 with n > 6 were recently found to be excellent precursors for the liquid phase deposition of silicon films. Herein we report the gramscale synthesis of the novel nona- and decasilanes (H3Si)(3)Si(SiH2)(n)Si(SiH3)(3) (2: n = 1, 5: n = 2) from (H3Si)(3)SiLi and Cl(SiPh2)(n)Cl by a combined salt elimination/dephenylation/hydrogenation approach. Structure elucidation of the target molecules was performed by NMR spectroscopy and X-ray crystallography. 2 and 5 are nonpyrophoric and exhibit a bathochromically shifted UV absorption compared to neo-pentasilane and the structurally related octasilane (H3Si)(3)SiSi-(SiH3)(3). TG-MS analysis elucidated increased decomposition temperatures and decreased ceramic yields for branched hydrosilanes relative to cyclopentasilane. Otherwise, very similar thermal properties were observed for hydrosilane oligomers with linear and branched structures.