One use of PIDA is in the preparation of similar reagents by substitution of the acetate groups. For example, it can be used to prepare (bis(trifluoroacetoxy)iodo)benzene (phenyliodine(III) bis(trifluoroacetate), PIFA) by heating in trifluoroacetic acid:
PIFA can be used to carry out the Hofmann rearrangement under mildly acidic conditions, rather than the strongly basic conditions traditionally used.  The Hofmann decarbonylation of an N-protected asparagine has been demonstrated with PIDA, providing a route to β-amino--alanine derivatives.
PIDA is also used in Suárez oxidation, where photolysis of hydroxy compounds in the presence of PIDA and iodine generates cyclic ethers. This has been used in several total syntheses, such as the total synthesis of (−)-majucin, (−)-Jiadifenoxolane A, and cephanolide A.