AbstractThe anionic polymerization of 1,3 and 1,4‐diisopropenylbenzene (DIB) was found to be characterized by a rather low ceiling temperature and by rather strong differences in reactivity between the two double bonds. At low degrees of conversion the polymers formed are essentially linear and carry one pendant double bond per monomeric unit. Branching and crosslinking can occur only at higher conversion. 1,3‐DIB can be copolymerized anionically with α‐methylstyrene. Grafting reactions were carried out on polymer backbones with pendant unsaturated groups, using two different pathways. The occurence of coupling reaction can be avoided by a proper choice of experimental cond