Abstract Block copolymers and blends comprised by liquid crystalline oligoester and polystyrene were prepared and their thermal stability were characterized by thermogravimetric analysis (TGA). The samples have shown three main decomposition temperatures due to (1) lost of flexible chain and decomposition of mesogenic segment, (2) decomposition of polystyrene and (3) final decomposition of oligoester rigid segment. Both copolymers and polymer blends presented lower thermal stability compared to polystyrene and oligoester. The residual mass after heating at 600 °C in copolymers and polymer blends were lower than those found in the oligoesters. A degradative process of aromatic segments of oligoester induced by decomposition of polystyrene is suggested.