Double emulsion (DE) droplets with controlled size and internal structure are a promising platform for biological analysis, chemical synthesis, and drug delivery systems. However, to further "democratize" their application, new methods that enable simple and precise spatial patterning of the surface wettability of droplet-generating microfluidic devices are still needed. Here, by leveraging the increase in hydrophilicity of polydimethylsiloxane (PDMS) due to the plasma-treatment used to permanently bond to glass, we developed a one-step method to selectively pattern the wettability of PDMS microfluidic devices for DE generation. Our results show that both Aquapel-treated and 1H,1H,2H,2H-Perfluorodecyltriethoxysilan (PFDTES)-treated devices are functionally showing the generality of our method. With the resulting microfluidic devices, both water-in-oil-in-water (w/o/w) and oil-in-water-in-oil (o/w/o) DE droplets can be produced. Using a PDMS mixture containing cross-linking agents, we formed PDMS microcapsules by solidifying the shell layer of water-in-PDMS-in-water DE droplets. We also characterize the morphological properties of the generated droplets/microcapsules. We anticipate the method developed in this work could be used in a broad range of applications of DE droplets.