Main observation and conclusionTwo discotic liquid crystalline (LC) molecules consisting of a bowl‐shaped corannulene core and five‐fold photoactive azobenzene branches with different paraffinic side chains were developed. Their self‐assembly, photo‐responsive behavior and charge‐carrier transport properties were investigated in detail. A wider mesophase temperature range was achieved when utilizing longer and furcal flexible side chain substitution. 2D XRD measurements revealed the π‐packed corannulene‐centered 1b (i.e., with furcal side alkoxyl chains) exhibited helical columnar LC phase. This packing structure also led to a higher hole charge carrier mobility of 7.07 x 10–2 cm2·V–1·s–1 compared to that of the counterpart 1a with linear side chain substitutions.