Droplet microfluidics has enabled the synthesis of polymeric particles with controlled sizes, shell thickness, and morphologies. Here, we report the Janus to core-shell structural evolution of biphasic droplets formed in a microfluidic flow-focusing device (MFFD) for the synthesis of polymer microcapsules with oil core/thickness-tunable shell via off-chip photo-and thermally induced polymerization. First, nanoliter-sized biphasic Janus droplets comprising an acrylate monomer and silicone oil were generated in a co-flowing aqueous polyvinyl alcohol (PVA) solution in an MFFD on a glass chip. Immediately following their break-off, the produced Janus droplets started to change their geometry from Janus to core-shell structure comprising a single silicone-oil core and an acrylatemonomer shell by the minimization of interfacial energy. Thus, we could produce monodisperse coreshell drops with average diameters of 105-325 μm, coefficient of variation (CV) values of 1.0-4.5%, and shell thickness of 1-67 μm. Subsequently, these drops were synthesized to fabricate polymeric microcapsules with tunable shell thickness via photo-and thermally induced polymerization. By increasing the concentration of the photo-and thermal initiator, we successfully produced thinner and ultra-thin shell (800 nm thickness) microcapsules. The surface structure of resulting particles was smooth in photopolymerization and porous in thermal polymerization. Microcapsules with core-shell structures, in which the active substances in cores are protected by the shells from the outer environment, have been applied in numerous fields such as foods 1,2 , cosmetics 3,4 , pharmaceutics 5 , printing 6,7 , and self-healing materials 8,9. Microcapsules can be synthesized via a variety of techniques including spray drying 10 , layer-by-layer deposition 11 , interfacial polymerization 12 , coacervation 13 , or membrane emulsification 14. Although these techniques can provide a high throughput, it remains difficult to fabricate uniform microcapsules with controlled size and high encapsulation efficiency. Recently, droplet microfluidics has been shown to provide a new and promising route to synthesize microcapsules. Using microfluidic technology, one can easily produce monodisperse core-shell droplets as ideal templates for fabricating microcapsules via subsequent various solidification methods; examples of the solidification methods include photo or thermally induced free-radical polymerization 15,16 , solvent evaporation 17 , freezing 18 , and ironic cross-linking 19. So far, the core-shell templates were prepared in two-step or one-step droplet formation. In the two-step method, using two T-junctions 20,21 , two flow-focusing junctions 22,23 , two co-flowing junctions 24 , or three-dimensional devices 25 , core drops are generated at first and then shell drops encapsulating these core drops are produced in a continuous phase as a separate step. Using this two-step approach, for example, acrylic capsules with aqueous cores with diameters of 10-340 µm and CVs ~5% ...