Novel T-shaped bolaamphiphiles consisting of a bent 2,5-diphenylethynyl thiophene rigid core with two terminal glycerol units and a lateral n-alkyl chain have been synthesized via Kumuda and Sonogashira coupling reactions as key steps. Their liquid crystalline behavior was investigated by polarizing optical microscopy(POM), differential scanning calorimetry(DSC), and X-ray diffraction(XRD). All such bolaamphiphiles can self-organize into square honeycomb LC phases with p4 mm symmetries in the presence of water. UV and PL measurements indicate fluorescent properties making them potential candidates for application in fluorescence sensor devices. Novel T-shaped bolaamphiphiles consisting of a bent 2,5-diphenylethynyl thiophene rigid core with two terminal glycerol units and a lateral n-alkyl chain have been synthesized via Kumuda and Sonogashira coupling reactions as key steps. Their liquid crystalline behavior was investigated by polarizing optical microscopy (POM), differential scanning calorimetry (DSC), and X-ray diffraction (XRD). All such bolaamphiphiles can self-organize into square honeycomb LC phases with p4 mm symmetries in the presence of water. UV and PL measurements indicative fluorescent properties making them potential candidates for application in fluorescence sensor devices.