The versatile crystal structure of tetragonal tungsten bronzes (A1₂A2₄C₄B10O30) can accommodate complex stoichiometries including cations in different valence states and vacant cation sites. Here, we report on the effect of thermally induced cation-vacancy disorder in the tetragonal tungsten bronze SrxBa1-xNb₂O₆ (SBNX). SBNX (x = 0.25, 0.33, 0.50, 0.61) ceramics, prepared by conventional solid-state synthesis, were annealed at varying temperatures and subsequently quenched to room temperature. The Curie temperature of all the SBNX materials increased with higher quenching temperatures, accompanied with ferroelectric hardening. The variation in thermal history also caused structural changes, specifically a contraction of the a lattice parameter and a minor elongation of the c parameter. These effects are discussed in relation to recent first principles calculations of the energy landscape of the cation-vacancy configurations and experimental evidence of thermally induced cation-vacancy disordering.