Abstract: A series of novel three-armed liquid crystals based on 1,3,5-trihydroxybenzene as a core and tw-[4-(p-alkoxybenzoloxy)phenoxycarbonyl]valeric acid as mesogenic arms were synthesized by aromatic esterification. They are a new kind of liquid crystals differing from conventional rod-like or discotic molecules. Their chemical structures were confirmed by FTIR and ¹HNMR spectra and their mesomorphic phase behavior was investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and thermograrimetric analyzer (TG). The results showed that the three-armed liquid crystals exhibit broad range of liquid crystalline phase at moderate temperature, and the mesomorphic ranges (Δt) broadens with increasing terminal alkyl chains. The temperatures at which the weight loss is up to 5% is higher than 340 t, which revealed that the synthesized three-armed liquid crystals are of high thermal stability. Threadlike texture, typical of nematic phase can be observed in the liquid crystalline state during heating/cooling process.