Electrophoresis 2014, 35, 2673–2680. DOI: 10.1002/elps.201400210 pH‐responsive microcapsules manufactured by combining electrostatic droplets (ESD) and microfluidic droplets (MFD) techniques to produce mono‐disperse core (alginate) ‐ shell (chitosan) structure with controlled drug release behavior. The fabricated core‐shell microcapsules have a pH‐controlled drug delivery function according to acidic and alkaline environment, and present positive biocompatibility, indicating their potential use in biological and biomedical applications, such as pH‐responsive drug‐delivery systems, scaffolding for bone tissues, and as an oral drug‐delivery vehicle.