In addition to simple oxidation of aromatic rings to form carbonyl compounds (see ), trifluoroperacetic acid can fully cleave the carbon–carbon bonds within the ring. Unlike other oxidations of alkylaromatic structures, which yield benzoic acids and related compounds by cleavage of the alkyl chain at the reactive benzylic position, trifluoroperacetic acid causes an "inverse oxidation", cleaving the aromatic ring itself while leaving the alkyl group intact.
This selectivity for certain types of bonds allows it to be used to decompose complex mixtures of hydrocarbons, such as coal, in order to determine structural details.
Aromatic systems containing heteroatoms are resistant to this ring-opening as heteroatom oxidation occurs preferentially and deactivates the ring towards electrophilic attack by the peroxy acid.  For example, purines, pyridines, and quinolines instead form N-oxides, while sulfur systems like octafluorodibenzothiophene are converted to sulfones.
Aromatic systems with ring-activating substituents can be oxidised to form phenols instead of undergoing a ring-opening reaction.  Mesitylene, for example, reacts with trifluoroperacetic acid to form mesitol (2,4,6-trimethylphenol).  Researchers attempting to form a lactone by Baeyer–Villiger oxidation of 7-oxodeacetamidocolchicine were unable to prepare the desired product, but did achieve oxidation of the aromatic ring to produce a phenol-derivative in high yield: