To develop materials with self-healing properties, polyurethane (PU) was modified with anthracene derivatives which endowed the PU films with a self-healing ability. The reversibility of the characteristic reaction, thermal performance and self-healing ability of PU anthracene (PUAn) films were systematically characterized by a series of experiments, showing that the synthesized PU elastomers were endowed with a satisfactory self-healing ability and reinforced thermal stability. Furthermore, the reversible degree of this characteristic reaction is as high as 35% and TGA analyses indicated that the decomposition temperature of the PUAn8 films was increased by 30 °C. Finally, the healing process took only a short time of about 40 min and the healing efficiency of PUAn8 was enhanced up to 94.84%. The results suggest that this system opened up the prospect for the development of self-healing materials.