Novel tetra- and hexacatenar materials based on benzobisthiazole derivatives have been synthesised (4a-c, 5a-c and 6a-c) and their mesomorphic properties have been studied by differential scanning calorimetry, polarised optical microscopy and X-ray diffraction. All compounds in series 4a-c display an enantiotropic hexagonal columnar phase, whereas their analogous compounds in series 5a-c did not show mesomorphic behaviour. Compound 6a displays an unidentified monotropic columnar phase, whereas compounds 6b and 6c show an enantiotropic rectangular columnar mesophase. The mesomorphic properties were found to be dependent on the length, position and number of alkoxy chains attached at the end of the rigid core. These compounds also show photoluminescence properties in the visible region and have good quantum yields. A thermogravimetric analysis was also performed.