A new organic-inorganic hybrid salt of cyclohexylammonium hexaisothiocyanatochromate(III) sesquihydrate, (C 6 H 11 NH 3 ) 3 [Cr-(NCS) 6 ] ⋅ 3/2H 2 O, was synthesized at room-temperature by metathesis and ligand addition for the establishment of energysaving chemical synthesis approach. The formation of this new salt was confirmed by FT-IR, UV-Vis spectrophotometry, elemental microanalysis, and single-crystal X-ray diffraction. The TGA study showed low-temperature thermal stability of this salt, where chromium oxide (Cr 2 O 3 ) formed under air and chromium sulfide (Cr 2 S 3 ) under argon, as PXRD confirmed their formation as nanocrystalline. The morphological studies by SEM and TEM revealed the formation of irregular polyhedron particles of Cr 2 O 3 and of hexagonal packed layers of Cr 2 S 3 . The textural study by nitrogen physisorption disclosed the mesoporous nature and high specific surface area of Cr 2 O 3 (∼ 132 m 2 g À 1 ) and Cr 2 S 3 (∼ 241 m 2 g À 1 ). Cyclohexylammonium could act as an organic self-template for the formation of mesopores and the high temperature of thermolysis assisted the formation of such pores.