Tristriazolotriazines with azobenzene substitution and peripheral alkoxy‐ or alkylamino chains were prepared from the corresponding aryltetrazoles and cyanuric chloride. These star‐shaped dyes are highly acidochromic. Alkoxy‐substitution allows reversible trans‐cis photoswitching. Compounds with a 3,4‐dialkoxy substitution are discotic liquid crystals that form broad and stable thermotropic mesophases. The thermal behavior was studied by DSC and polarizing optical microscopy.