Regular arrays of colloidal particles can produce striking structural colors without the need for any chemical pigments. Regular arrays of colloidal particles can be processed into microparticles via emulsion templates for use as structural colorants. Photonic microparticles, however, suffer from intense incoherent scattering and lack of suspension stability. We propose a microfluidic technique to generate hydrogel-shelled photonic microspheres that display enhanced color saturation and suspension stability. We created these microspheres using oil-in-water-in-oil (O/W/O) double-emulsion droplets with well-defined dimensions with a capillary microfluidic device. The inner oil droplet contains silica particles in a photocurable monomer, while the middle water droplet carries the hydrogel precursor. Within the inner oil droplet, silica particles arrange into crystalline arrays due to solvation-layer-induced interparticle repulsion. UV irradiation solidifies the inner photonic core and the outer hydrogel shell. The hydrogel shell reduces white scattering and enhances the suspension stability in water. Notably, the hydrogel precursor in the water droplet aids in maintaining the solvation layer, resulting in enhanced crystallinity and richer colors compared with microspheres from O/W single-emulsion droplets. These hydrogel-encased photonic microspheres show promise as structural colorants in water-based inks and polymer composites.