When using initially a W/O microemulsion, encapsulation of hydrosoluble chemicals can be achieved in the inner aqueous droplet of the double emulsion. We showed, combining singledrop experiments, microscopy and rheology, that water diffuses from the outer continuous phase into the oily droplet, hydrating hydrosoluble polymers present in it and forming an aqueous droplet in the oil droplet after equilibration of the osmotic pressure. Additionally, we observe that deprotonated PNIPAMcarboxylate co-dispersed with PEG in octanol allows stabilization of multiple core double emulsions that transform into single core double emulsion when pH is decreased to reprotonate that polymer. We believe these findings could be of interest for materials chemistry and microencapsulation applications.