Two crystalline open-framework indium phosphites (denoted SCU-31 and SCU-32) were prepared using amino acids as structure-directing agents. They have isoreticular pillared-layered structures built up from 6 × 1 and 4 = 1 clusters. Notably, the two compounds show excellent water stability and exhibit blue fluorescence under UV light irradiation at room temperature. The proton-conducting behaviour of SCU-31 was also investigated.