Ceramic coatings have positive feedback to annealing treatment, but improper annealing treatment can also bring disastrous consequences. In this article, a thick TiN coating without a bonding layer was prepared by reactive plasma spraying technology and then subjected to heat treatment at three different temperatures in atmospheric and argon atmospheres. By exploring the hardness, modulus, and corrosion resistance of the coatings, combined with analysis of microstructure, phase composition, and interatomic bonding conditions, it was found that the TiN coating exhibited the lowest porosity after atmospheric heat treated at 500 °C. Meanwhile, it also showed the highest hardness, modulus, and optimal corrosion resistance. After heat treated at 650 °C in the atmosphere, the protective performance of the coating was decreased, but it was still far superior to the as-sprayed coating. The coating after heat treated in the argon atmosphere did not achieve ideal performance. The coating heat treated at 650 °C even exhibited inferior comprehensive performance to the as-sprayed coating. Therefore, it was summarized that the atmospheric environments and the temperature above the phase transition temperature were suitable for obtaining the optimal TiN coating.