New organic-inorganic hybrids have been synthesized by the intercalation of n-alkylamines (methylamine, ethylamine, n-propylamine, n-butylamine, n-hexylamine, and n-octylamine) into the structure of the protonated and hydrated form of the perovskite-like layered titanate H₂K_0.5Bi_2.5Ti₄O₁₃·H₂O (HKBT₄·H₂O). The possibility of the synthesis of the hybrid materials was studied in a wide range of conditions. It was found that interlayer water plays a crucial role in the formation of intercalated hybrids. The obtained compounds were characterized with powder X-ray diffraction analysis; Raman, IR, and NMR spectroscopies; thermogravimetry (TG), TG coupled with mass spectrometry, and CHN analyses; and scanning electron microscopy. It was suggested that the intercalated n-alkylamines exist in the form of alkylammonium ions forming a paraffin-like bilayer with an average tilting angle of ∼77.5°. The obtained HKBT₄×RNH₂ compounds contain 0.4-0.7 n-alkylamine molecules per formula unit as well as the varied amount of intercalated water. By gentle heating, they can be obtained as dehydrated forms, which are thermally stable up to 250 °C.