AbstractThe dielectric properties of the siloxane side‐chain liquid‐crystal (LC) copolymer 1 were investigated using high‐frequency techniques. The copolymer could be aligned homeotropically either by cooling from the melt with the aligning electric field on or by application of the field whilst the sample was in the LC state. Using the latter method the kinetics of the homeotropic alignment process could be determined. Samples of different purity were used and the kinetics and steady‐state properties compared and a strong dependence on polymer purity was found in both cases. Fuoss‐Kirkwood deconvolution of the relaxation peaks allowed examination of the fundamental motion of the mesogenic units.