Ultrafast optical Kerr effect spectroscopy has been used to study the temperature-dependent orientational dynamics of 1,n-dicyano n-alkane liquids ranging from dicyanomethane to 1,8-dicyanooctane. The dependence of the reorientational times on temperature and viscosity is consistent with the molecules adopting a largely extended structure in the liquid state, with a preference for gauche conformations at the methylenes bonded to the cyanide groups. The data are also suggestive of temperature-dependent, collective structural rearrangements in these liquids.