The temperature dependence of electron spin polarization and intensity in low‐energy electron diffraction (LEED) from a clean W(001) surface has been measured over the range 1000°–300°C. The effect of temperature on polarization is found to be greatest at energies for which the intensity is low and the polarization, and rate of change of polarization with energy, is large. The present results may be interpreted in terms of a shift of polarization features toward lower energies as a result of thermal expansion when the crystal is heated.