A microfluidic device having both hydrophobic and hydrophilic components is exploited for productionof multiple-phase emulsions. For producing water-in-oil-in-water (W/O/W) dispersions, aqueous dropletsruptured at the upstream hydrophobic junction are enclosed within organic droplets formed at thedownstream hydrophilic junction. Droplets produced at each junction could have narrow size distributionswith coefficients of variation in diameter of less than 3%. Control of the flow conditions produces variationsin internal/external droplet sizes and in the internal droplet number. Both W/O/W emulsions (with twotypes of internal droplets) and oil-in-water-in-oil emulsions were prepared by varying geometry andwettability in microchannels.