In　this　paper,　we　report　a　new　method　for　preparing　bottlebrush　polymers　(BBPs)　with　a　polyvinyl　ether　(PVE)　backbone　using　a　combination　of　cationic　polymerization　and　atom　transfer　radical　polymerization　(ATRP).　A　Br-functionalized　vinyl　ether　monomer,　2-vinyloxyethyl-2-bromoisobutyrate　(VEBB),　was　synthesized　for　the　＂grafting-from＂　synthesis　of　BBPs,　and　it　can　readily　undergo　cationic　polymerization　in　the　presence　of　an　organic　Br　&　oslash;nsted　acid　and　allow　for　subsequent　ATRP　of　different　monomers　to　introduce　side　chains.　Accordingly,　a　series　of　bottlebrush　polymers　with　a　well-defined　backbone　and　different　side　chains　can　be　prepared　via　this　combination　of　cationic　polymerization　and　ATRP　technology.　The　thermal　transition　of　PVE-based　bottlebrush　polymers　was　studied　by　differential　scanning　calorimetry　(DSC).　The　surface　morphologies　and　aggregation　behaviours　of　these　nanoscopic　single　molecules　were　studied　by　tapping-mode　atomic　force　microscopy　(AFM)　on　mica.