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The crystal structure and electron density of tetraphenyl-silicon, (C 6 H 5 ) 4 Si, ( a  0  = 11.450(2),  c  0  = 7.063(1) Å,  P [unk]2 1  c ,  Z  = 2) has been studied by single crystal X-ray diffraction. Data were collected up to 2 θ  max  = 70° ( s  max  = 0.81 Å −1 ). The final agreement factors of the all-data refinement were  R  overall  = 0.027 and  R  w  = 0.033 (omitting unobserved intensities). The electron redistribution due to chemical bonding was studied by calculating (X – X HO ) difference density maps with the atomic parameters from a semi-high-order (HO) refinement with reflections of  s  &gt; 0.48 Å −1 . The deformation density distribution associated with the Si – C bond compares qualitatively well with the Si – O bonds found in forsterite, Mg 2 SiO 4 , and quartz, SiO 2 .