Thin films composed of titanium nitride doped with silver were deposited by DC reactive sputtering, with Ag contents varying between 0 and 50 at.%. The as-deposited samples were subjected to vacuum annealing treatments, with a range of temperatures varying from 200 to 500 °C, in order to study the morphological and structural changes that may occur. The as-deposited samples showed three main zones of basic characteristics, which differ both in terms of morphology and structural features. By increasing the annealing temperature, the thermodynamic stability is accelerated, giving rise to (i) a uniform dispersion of silver particles at 200 °C; (ii) the start of segregation at 300 °C; (iii) at 400 °C the coalescence of the segregated Ag particles takes place and finally (iv) at 500 °C the formation of large Ag clusters is evident, particularly within the zone that comprises the samples with higher Ag content. In addition to corroborate the presence of free Ag in Ag:TiN thin films, the increasing annealing temperature promotes the improvement of the coating's crystallinity, as well as Ag grain growth.