A protonated form of the n = 4 layered bismuth containing perovskite-like titanate K_2.5Bi_2.5Ti₄O₁₃ belonging to Ruddlesden-Popper phases was prepared via ion exchange reaction of interlayer K⁺ with protons. Its composition was investigated by TG ICP and EDX analysis was found to be H₂K_0.5Bi_2.5Ti₄O₁₃·H₂O. The thermal behavior of the obtained phase was investigated by STA coupled with mass-spectrometry, the structural changes, happening with the sample during heating, were examined by XRD. It was shown that the as-prepared hydrated phase undergoes two-stage dehydration at low temperatures (up to 160 °C). The further heating leads to the gradual decomposition and crystallization of new phases, notably Bi₂Ti₂O₇, Bi₄Ti₃O₁₂ and Bi₂Ti₄O₁₁. The morphology of the as-prepared sample and samples after heat treatment was examined using SEM.