AbstractThe tristriazolotriazine (TTT) N‐heterocycle, despite being a relatively new mesogenic core for use in discotic liquid crystals, has already demonstrated its importance and promising characteristics. In this work, we extended the knowledge about the TTT, increasing the core size with alkoxybenzoate units, as well as evaluating how the expansion and number of peripheral chains affected the thermal and photophysical properties, both in solution and spin‐coated films. Their thermal behaviour and self‐assembly were studied by differential scanning calorimetry, polarizing optical microscopy and X‐ray diffraction with synchrotron radiation, while the photophysics was investigated by UV‐Vis absorption and fluorescence spectroscopy. The results show that, despite a considerable decrease in the fluorescence quantum yield with the core expansion, the mesomorphic properties are significantly enhanced, with two products showing Colh mesophase at room temperature, with large range of mesomorphism and very good thermal stability. It was also demonstrated how structural changes affected the self‐assembly properties.