Cross sections &sgr; for the photoionization of metastable rare‐gas atoms (He*‐Xe*) over a wide range of photon energies are presented. In marked contrast to that found for He* where &sgr;∼10−18cm2and decreases monotonically with photon energy, the cross sections &sgr; for Ne*‐Xe* are much smaller ∼10−19cm2and exhibit optical windows within the wavelength range 2000–3000 A˚ of current laser interest.