Amphiphilic-hyperbranched polyglycidols and a linear analogue were tested for the unimolecular elimination (E1) reactions of tert-alkyl iodides. Their encapsulation properties were also compared. The linear polymer was found to have very good "unimolecular reverse micellar" characteristics as well, even though the results showed the advantages of a hyperbranched nature over a one linear one. Our results showed the need for a direct comparison of branched and linear polymers for any application.