Utilizing the unique solubility of poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC), which is soluble in only water and alcohol, we synthesized a water-soluble block copolymer emulsifier composed of a hydrophilic PMPC block and an amphiphilic poly[oligo(ethylene glycol) methacrylate] (POEGMA) block via reversible addition-fragmentation chain transfer (RAFT) polymerization. Water in-oil (W/O) emulsions were successfully formed in the presence of the resulting PMPC-b-POEGMA, which acted as a stabilizer of water droplets in a chloroform continuous phase because the PMPC and POEGMA blocks were distributed to the water and chloroform phases, respectively. Next, the amphiphilic poly[poly(ethylene glycol) methacrylate] (PPEGMA) gel layer, which contained bis(2-methacryloyl)oxyethyl disulfide as a reductively responsive cross-linker, was prepared by inverse miniemulsion periphery RAFT polymerization from the PMPC-b-POEGMA that stabilized the W/O emulsions. The resulting PPEGMA gel capsules were colloidally stable in not only chloroform but also water without additional hydrophilic surface modification. The drug-release behavior from the PPEGMA gel capsules in response to dithiothreitol (DTT), which is a reducing agent, was investigated using fluorescein-conjugated dextran (FITC-Dex) as a model drug. The FITC-Dex release rate from the gel capsules in a phosphate buffer solution (pH 7.4, 20 mM) with DTT was fast compared to that without DTT. The reductively responsive FITC-Dex release is attributed to the cleavage of disulfide bonds that act as cross-links in the PPEGMA gel layer. The fascinating properties of the PPEGMA gel capsules suggest that they can provide a useful platform for designing drug carriers for protein and gene delivery and nanobioreactors.