We report liquid crystalline systems constructed by the hierarchical supramolecular self-organization of various substituted benzoic acid derivatives as the building blocks. Discotic lamellar and rectangular columnar phases and smectic phase were observed for the mixed liquid crystal systems consisting of 4-(1,3-alkadiynyl)benzoic acids (mPhDA), 4-(1-alkynyl)benzoic acids (mPhA), and 4-alkoxybenzoic acids (mOBA) as the components.