A number of dendrons of various chain lengths derived from the esters of 3,4,5-tris(tetrade-cyloxy)benzoic acid were synthesized. These esters were used as building blocks in the design of polyester molecules. Intermediate products, such as branched compounds with variation of functional groups in focal point (aromatic acids and their benzyl esters, aldehydes of different generation) were obtained. The structure and purity of all the compounds were determined by elemental analysis, FT-IR, NMR spectroscopy, mass spectrometry (MALDI-ToF). The phase behavior was investigated by differential scanning calorimetry and confirmed by polarized optical microscopy. Consequently, it was established that the liquid-crystalline properties of this series of dendrons arise from the degree of branching. This behavior can be explained by the formation of hydrogen bonds, as well as microsegregation processes of the links of the macromolecule.