Hyperbranched liquid crystalline polymers with azomesogenic and cholesteryl groups in their terminal positions were designed and synthesized by direct polycondensation reaction. The chemical structures and thermal and mesomorphic properties of the synthesized polymers were investigated by FT-IR, 1H-NMR, differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), and polarizing optical microscopy (POM). The inherent viscosities (ηinh) of the polymers were measured to be between 0.30 and 0.50 dL/g in phenol/p-chlorophenol/1,1,2,2-tetrachloroethane (25/40/35 = w/w/w). The degree of branching (DB) in these polymers ranged from 0.37 to 0.75; they, as amorphous polymer, showed glass transition temperatures ranging from 80 to 120 °C; the polymers readily dissolved in most of the organic solvents used in the experiments. Only hyperbranched polymers with a cholesteryl group as their mesogenic group showed liquid crystalline phases.