Photochemical isomerization of azobenzene intercalated in the hydrophobic, interlayer spaces of swelling fluor-tetrasilicic micas exchanged with dialkyldimethylammonium ions, with the alkyl chain length from 10 to 18, was investigated. Thin films of the organoammonium-mica-azobenzene intercalation compounds were obtained by depositing a suspension of the organoammonium-micas (prepared using a toluene/methanol solution of azobenzene) on quartz substrates. The intercalated azobenzene showed reversible photochromic reactions induced by UV and visible light irradiation. The fraction of the photochemically formed cis-isomer in the photostationary states decreased with a decrease in temperature. The observed change in the photochemical reactions is thought to reflect changes in the states of the dialkyldimethylammonium ions in the interlayer space of the swelling fluor-tetrasilicic mica.