The X-ray structural characterization of the iron(III) hexa­fluoro­acetyl­acetonate high-tem­per­a­ture polymorph reveals its structure as trigonal, which is different from the previously reported monoclinic low-tem­per­a­ture polymorph. The transformation between the two polymorphs was studied upon crystallization from the gas phase, melt, and from solution at different tem­per­a­tures.