Polyphenylsilane, (HSiC6H5)(n), was synthesised by catalytic coupling of phenylsilane using Cp(2)ZrCl(2)nBuLi as a catalyst. Chlorination of the resulting polymer with tetrachloromethane (CCl4) gave polychlorophenylsilane, (ClSiC6H5)(n), subsequent substitution of chloride by dimethylamine yielded polydimethylaminophenylsilane, ((CH3)(2)NSiC6H5)(n) The X-ray pattern of the three polysilanes reveal their amorphous state. Due to the similarity of the X-ray pattern of the three polysilanes, diffraction peaks are observed at s similar to 0.6, 1.4 and 3.3 Angstrom(-1), similar conformation and packing of the polysilane chains are concluded. The peaks at 0.6 Angstrom(-1) are identified as interchain peaks. From a comparison of the reduced scattering functions of polyphenylsilane and liquid benzene, we conclude that the arrangement of phenyl rings in polyphenylsilane is comparable to the statistical disorder of benzene molecules in the liquid state.