The process of acylation of aromatic ring was found to be a sole reaction direction upon photolysis of trim ethylacetyl and valeroyl iodides RCOI (R= n Bu, tert Bu) in toluene medium. The photochemical reaction of toluene with valeroyl iodide and pivaloyl iodide begins with acylation of the phenyl group. However, aryl alkyl ketones RCOC6H4Me formed at this stage proved to be only intermediates in the studied photo chemical processes.