Various novel block cationomers consisting of polyisobutylene (PIB) and poly [2-(dimethylamino)ethyl methacrylate] (PDMAEMA) segments were synthesized and characterized. The specific targets were various molecular weight diblocks (PIB-b-PDMAEMA(+)) and triblocks (PDMAEMA(+)-b-PIB-b-PDMAEMA(+)), with the PIB blocks in the DPn = 50-200 range (number-average molecular weight = 3,000-9000 g/mol) connected to blocks of PDMAEMA(+) cations in the DPn = 5-20 range (where DP is the number-average degree of polymerization). The overall synthetic strategy for the preparation of these block cationomers had four steps: (1) synthesis by living cationic polymerization of mono- and diallyltelechelic polyisobutylenes, (2) end-group transformation to obtain PIBs fitted with termini capable of mediating the atom transfer radical polymerization (ATRP) of DMAEMA, (3) ATRP of DMAEMA, and (4) quaternization of PDMAEMA to PDMAEMA I-+(-) by CH3I. Scheme 1 shows the microarchitecture and outlines the synthesis route. Kinetic and model experiments provided guidance for developing convenient synthesis methods. The microarchitecture of PIB-PDMAEMA di- and triblocks and the corresponding block cationomers were confirmed by H-1 NMR and FTIR spectroscopy and solubility studies.