The phase transition of urea complexes whose guest components range from n-paraffin to polyethylene was investigated by DSC thermal analysis. The transition temperatures increased with increasing the chain length; the related heats did not change much with the chain length. An X-ray powder diffractometry for urea-polyethylene complex revealed that the complex undergoes the same kind of phase transition between orthorhombic and hexagonal as urea-n-paraffin complex. The transition is interpreted in terms of an order-disorder transition with respect to the orientation of the guest molecule.