Crosslinked polystyrene resins containing pendant benzyl acrylate or chiral acrylates reacted with 1,3-butadiene or 2,3-dimenthyl-1,3-butadiene in the presence of the Lewis acid catalysts to yield Diels-Alder adducts. The polymer-bound Diels-Alder reactions were compared with their analogous reactions in solution. In reactions leading to optically active products the enantiomeric excesses on the polymer were at least as high as those performed in solution.