Though great attention has been paid in constructing well-defined nano-structures via the self-assembly of amphiphilic macromolecules, the self-assembly of non-amphiphilic macromolecules in nanodroplet has drawn less attention up to now. Recently, we prepared a temperature-responsive PEG-based branched polymer with disulfide bonds in its backbone via reversible addition-fragmentation chain transfer (RAFT) polymerization of 2-(2-methoxyethoxy) ethyl methacrylate, oligo(ethylene glycol) methacrylate, and N,N-cystamine bisacrylamide. Subsequently, we loaded the branched polymer into nanodroplets, and have found that the self-assembly behaviors of this branched polymer in the nanodroplet are different from those in common solution. Bioreducible nanocapsules with tunable size can easily formed in nanodroplet even at high concentration.