The possibility to prepare new organic-inorganic hybrids by grafting reactions of the protonated perovskite-like oxide H₂K_0.5Bi_2.5Ti₄O₁₃·H₂O (HKBT₄·H₂O) with n-alcohols (with alkyl chain length n_c = 1–4, 6, 10) has been studied. The reactions have been conducted by grafting using preliminarily n-butylamine and n-octylamine intercalated derivatives of HKBT₄ and in the case of n-decanol, the alcohol exchange approach of shorter-chain alcohols substitution has been also performed. Grafting reactions have been conducted at various temperatures with a view to fully substitution the n-alkylamine by n-alcohols. The obtained samples have been characterized by powder XRD analysis, NMR spectroscopy, CHN analysis, and SEM. The thermal stability has been studied by thermogravimetric analysis. It was shown that the pure methanol and ethanol hybrids could not be obtained in conditions tested and the optimal conditions of preparation of other n-alcohol hybrids have been established. In addition, it was shown that the HKBT₄ compound is easily subjected to bismuth reduction at high temperatures, leading to the destruction of the perovskite-like structure.