The effect of annealing in air on internal structure and optical properties of hot filament CVD nanocrystalline diamond films was investigated. Oxidation of the films lead to selective removal of intercrystallite layers with formation of highly porous structure with characteristic dimensions of several nanometers. Dramatic changes in optical transmission and Raman spectra were also observed. The origin of the two Raman spectrum maxima at 1140 and 500 cm−1 is discussed. Hydrogen absorption and desorption processes in porous diamond were studied.