Iodosobenzene is prepared from iodobenzene. It is prepared by first oxidizing iodobenzene by peracetic acid.  Hydrolysis of resulting diacetate affords "PhIO":
The structure of iodosobenzene has been verified by crystallographically. Related derivatives are also oligomeric. Its low solubility in most solvents and vibrational spectroscopy indicate that it is not molecular, but is polymeric, consisting of –I–O–I–O– chains. The related diacetate, , illustrates the ability of iodine(III) to adopt a T-shaped geometry without multiple bonds. 
Theoretical studies show that the bonding between the iodine and oxygen atoms in iodosobenzene represents a single dative I-O sigma bond, confirming the absence of the double I=O bond.
A monomeric derivative iodosylbenzene is known in the form of 2-(tert-butylsulfonyl)iodosylbenzene, a yellow solid.  C-I-O angle is 94.78°, C-I and I-O distances are 2.128 and 1.848 Å.