As　one　of　the　hot　research　topics　in　the　field　of　polymer　chemistry,　bottlebrush　polymer　is　a　class　of　polymeric　materials　with　special　molecular　structures　that　can　be　precisely　and　flexibly　controlled　in　terms　of　nanostructure　and　shape.　A　＂grafting-from＂　strategy　using　in　situ　halogen　exchange　and　reversible　chain　transfer　catalyzed　polymerization　(RTCP)　was　developed　to　synthesize　amphiphilic　bottlebrush　polymer　(PBIEMA-g-PBzMA)-b-PPEGMEMA.　The　bottlebrush　polymer　self-assemble　in　aqueous　solution　to　form　spherical　vesicles,　in　which　hydrophilic　PPEGMEMA　chains　forming　the　crown　structure　of　the　micelles,　and　hydrophobic　PBIEMA　chains　and　PBzMA　chains　generating　the　core.　The　feature　provides　(PBIEMA-g-PBzMA)-b-PPEGMEMA　to　encapsulate　the　hydrophobic　pyrene　and　the　hydrophilic　R6G　either　individually　or　simultaneously.　This　work　offers　a　new　platform　to　design　and　synthesize　amphiphilic　bottlebrush　polymer　through　a　metal-free　process.　©　2023,　The　Polymer　Society,　Taipei.