Abstract The effect of processing protocol on physical stability and the microstructure of water‐in‐oil‐in‐water multiple emulsions containing a mixture of two amphiphilic copolymers with opposed hydrophilic‐lipophilic balance as emulsifiers and a green solvent, 2‐ethylhexyl lactate, as the dispersed phase, has been assessed. Emulsions were obtained in at least two steps: a homogenization step by using a rotor‐stator device, followed by one or two homogenization steps carried out in a high‐pressure device that used microfluidizer technology. To study the microstructure and physical stability of these emulsions, a combination of different techniques, such as transmitted‐light optical microscopy, globule size distribution, viscous flow tests, and multiple light scattering measurements, were performed.