Although less famous than low-spin trivalent cobalt found in [CoIII(NH3)6xClx]Cl3x (x 3), which was exploited by Alfred Werner during the early part of the 20th century for establishing the basic rules of coordination chemistry, related trivalent chromium complexes exhibit comparable kinetic inertness, a rare property along the 3d-transition series. The associated slow isomerisation processes are compatible with the isolation of well-defined heteroleptic complexes. Some subtle energetic differences between CrIII-X (X = halide, pseudo-halide, cyanide, solvent) and Cr-N bonds can be exploited for preparing stable and inert cis/trans-[Cr(N \ N)2X2]+ and fac/mer-[Cr(N \ N \ N)X3] primary heteroleptic complexes incorporating multidentate nitrogen-containing chelate ligands. The use of these building blocks within the frame of the ‘complex-as-ligand’ strategy, or via the labilization of the remaining Cr-X bonds pave the way for the design of discrete polymetallic assemblies in which the photophysically appealing [CrIIIN6] chromophores could find applications as functional light-converting devices.