We observed the emission of correlated electron pairs from the valence band of solids following the absorption of single photons in the vacuum ultraviolet range. Applying a time-of-flight technique, we measured the energy distributions of correlated electron pairs emitted from clean Cu(001) and Ni(001) crystals. Significant differences between both metals were found. For the interpretation we suggest a single step two-electron-photoionization process and a competing two step mechanism involving a single photoionization and a subsequent electron-electron collision in the valence band.