Polystyrene and polyacrolein were prepared using divinylbenzene (DVB) and tetraethylene glycol diacrylate (TEGDA) as crosslinking agents with varying extents of crosslinking. These polymeric supports were used to prepare acyl transfer reagents like oximino esters and oximino dithiocarbonic anhydrides. The reactivity of the acylating function was determined as a function of the varying macromolecular characters. Investigations revealed a significant influence of the nature of macromolecular support, nature and extent of crosslinking, and the chemical environment of the reagent functions in deciding the extent of the acyl transfer reaction. In the case of DVB crosslinked reagents, the reactivity decreased with increase in the extent of crosslinking, whereas in the case of TEGDA crosslinked reagents, the reactivity increased up to 4% crosslinking and then decreased as the degree of crosslinking was increased.