Perylo[1,12-b,c,d] thiophene tetraesters exhibiting wide range hexagonal columnar phase have teen. synthesized. These compounds also exhibit good homeotropic alignment in the liquid-crystalline phase which is very important for the device fabrication. These compounds.: showed sky-blue luminescence in solution under the long-wavelength UV light. With high solubility and high quantum yield these,compounds can serve as standard's to measure quantum yields of unknown samples. This new class of materials is promising, considering the emissive nature and Stabilization of hexagonal columnar mesophase over a wide thermal range and ease of synthesis.