Reversible　chain　transfer　catalyzed　polymerization　(RTCP)　is　a　practical　and　efficient　process　for　the　precise　synthesis　of　polymers　with　special　architecture　by　using　simple　phenols　(2,4,6-trimethylphenol,　TMP)　or　hydrocarbons　(xanthene,　XT)　as　efficient　organocatalysts.　Herein,　alkyl　iodide　(R-I),　which　was　generated　from　in　situ　bromine-iodine　transformation　of　alkyl　bromide　(R-Br)　with　sodium　iodide　(NaI),　was　served　as　initiator　to　mediate　RTCP　with　TMP　or　XT.　MMA　and　other　functional　methacrylates,　including　GMA,　DEAM,　DMAEMA　and　BzMA,　were　successfully　initiated　by　combining　organocatalysts　and　azo　initiators　to　yield　polymers　with　low-polydispersity　(Mw/Mn=1.1–1.5)　and　ideal　monomer　conversions　(50%–90%)　at　moderate　temperature.　Moreover,　3-armstar　polymers　were　also　obtained　by　this　method.　The　high　chain-end　fidelity　of　the　obtained　poly(methyl　methacrylate)　with　iodine　as　chain-end　group　(PMMA-I)　was　confirmed　by　chain-extension　reaction.　The　environmentally　friendly　initiators　and　organocatalysts　exhibit　powerful　polymerization　properties　toward　RTCP,　providing　a　significant　method　to　synthesize　functional　polymers.　©　2021,　Chinese　Chemical　Society　Institute　of　Chemistry,　Chinese　Academy　of　Sciences.