Multiple w/o/w emulsions (MEs) are promising systems for protecting fragile hydrophilic drugs and controlling their release. We explore the capacity of a single pH-sensitive copolymer, PDMS60-b-PDMAEMA50, and salts, to form and stabilize MEs loaded with sucrose or catechin by a one-step mechanical process or a microfluidic method. ME cytotoxicity was evaluated in various conditions of pH. Using the mechanical process, the most stable emulsions were obtained with Miglyol®812 N and isopropyl myristate in a final pH range of 8–12 and [0.3 M−1 M] NaCl concentrations. Conversely, with the microfluidic method, isopropyl myristate at pH 3 without salt was more efficient. Catechin strongly affected the formation of droplets by the mechanical process but did not modify the conditions of stability of MEs obtained by the microfluidic method. The antioxidant power of catechin was preserved in the inner droplets, even in emulsions prepared by the mechanical method at pH 8. An incomplete release of sucrose and catechin from the emulsions was observed and attributed to the interaction of molecules with the copolymer through hydrogen bonding. This study highlights some of the barriers to break to formulate multiple emulsions stabilized by a PDMS-b-PDMAEMA copolymer or other polymers which can form hydrogen bonds interaction with encapsulated drugs.