A layered perovskite-type oxide intercalated with n-butylamine is reported as an efficient photocatalyst for hydrogen production from aqueous solutions of alcohols for the first time. The hybrid photocatalyst H₂Nd₂Ti₃O₁₀×BuNH₂ was synthesized by solid-state ceramic method followed by protonation, intercalation of methylamine and subsequent substitution by n-butylamine. The product was characterized by powder XRD, TGA, STA-MS, DRS, IR, and Raman spectroscopy, CHN analysis, SEM. Intercalation of n-butylamine caused a dramatic increase in photocatalytic activity of H₂Nd₂Ti₃O₁₀ in the reaction of hydrogen evolution from aqueous solutions of methanol, ethanol, and n-butanol under UV radiation. While the non-intercalated Pt-loaded H₂Nd₂Ti₃O₁₀ showed a maximum quantum efficiency of only 2% in the 220–340 nm range, the efficiency for hybrid samples reached 23% under the same conditions and after variation of experimental parameters even 52% efficiency was achieved. This effect may be associated with the significant expansion of the interlayer space, which is considered as a separate reaction zone.