The aim of this work is the achievement of nanostructured TiC–TiB2 powders through a metastability approach based on the Self–propagating High–temperature Synthesis (SHS) process followed by quench to obtain highly metastable powder agglomerates. An optimisation of the reaction stoichiometry was carried out in order to obtain products with approximately eutectic composition (i.e. 67%mol TiC – 33%mol TiB2). An optimized amount of sodium borate was used as gasifying additive to produce dispersed nanostructured powder agglomerates. The metastability of the nanocomposite powders obtained through the (SHS+quench) route was evaluated by annealing. The morphological evolution of the powders after thermal treatment yielded a recrystallisation with limited grain growth of the nanostructured TiC–TiB2 phases and demonstrated the metastability of the products obtained by the (SHS+quench) route.