A new organozincate-mediated anionic polymerization that was developed by using tBu4ZnLi2 as an initiator was discussed. This anionic polymerization had a high compatibility with protic solvents that accelerated the reactions. This method was free from any requirement for the protection of acidic protons or strictly anhydrous reaction conditions. The polymer growth was well-regulated and the terminal zincate of the polymer end could be modified by electrophilic traps. The method posed great versatility and high chemoselectivity and multifunctionalized monomers such as NIPAm, DMA, AN and HEMA could be polymerized in high yields.