Inorganic–organic hybrid compounds of the amino acid alanine have been prepared and characterized for the first time. Thus by the reaction of β-alanine with copper salts, one-dimensional hybrid chain compounds of the formulae [Cu(CO₂CH₂CH₂NH₃)Cl₂], I, and [Cu(H₂O)₂(NH₃CH₂CH₂CO₂)][SO₄]·H₂O, II, and a two-dimensional layered compound [NH₄]_0.33[Cu_0.5(CO₂CH₂CH₂NH₂)Cl_0.33]·H₂O, III, have been obtained and their structures established by X-ray crystallography and other techniques. Hybrid chain alaninates of lead and strontium of the formulae [Pb(CO₂CH₂CH₂NH₃)₂(NO₃)₂], IV and [Sr(CO₂CH₂CH₂NH₃)₂(NO₃)₂], V have also been obtained by the reaction of the corresponding metal salts with alanine. The linear chain compounds, I, II, IV and V contain extended metal–X–metal (X = Cl or O) bonds and have the I¹O⁰ type inorganic (I) and organic (O) connectivities. The layered compound III also has metal–X–metal bonds with I²O⁰ type connectivity. Interestingly, the zero-dimensional copper alaninate dimer of the composition [Cu₂(CO₂CH₂CH₂NH₃)₄Cl₂]·2Cl·H₂O can be transformed to the linear chain structure I or the layered structure III under mild conditions.