The molecular structure of phenyl silyl ether C6H5OSiH3 has been studied by the sector-microphotometer method of electron diffraction. The Si—O bond length is 1.648 ± 0.007 Å, the C—O bond length is 1.357 ± 0.009 Å, the Si—O—C angle is 121 ± 1° and the dihedral angle between the Si—O—C plane and the aromatic ring is 68 ± 3°. These results are discussed and compared with those for similar molecules.