The stability and size of poly(lactic-co-glycolic)acid (PLGA)-containing double emulsions and the resulting PLGA microcapsules are controlled by varying the composition of highly monodisperse water-in-oil-in-water (W/O/W) double emulsions. We propose that the basic inner phase of W/O/W double emulsions catalyzes the hydrolysis of PLGA and the ionization of carboxylic acid end groups, which enhances the surface activity of PLGA and facilitates the stabilization of the double emulsions. The size of PLGA-containing double emulsions and that of resulting microcapsules can be readily tuned by osmotic annealing, which depends on the concentration ratio of a solute in the inner and outer phases of double emulsions. The internal volume of PLGA microcapsules can be changed by more than 3 orders of magnitude using this method. This approach also overcomes the difficulty in generating monodisperse double emulsions and microcapsules over a wide range of dimensions using a single microfluidic device. The osmotic annealing method can also be used to concentrate encapsulated species such as colloidal suspensions and biomacromolecules.