We summarize recent developments in x-ray microscopy of polymers by focusing on the characterization of organic electronic devices. The quantitative compositions of model polymer blends have been mapped at a resolution of ∼35 nm. Since it could be inferred that these devices have structures smaller than 35 nm, quantitative compositional mapping at length scales below the present resolution limit of x-ray microscopy is required. Organic devices thus serve to both highlight the success of NEXAFS microscopy to date, but to also outline the very real need for higher spatial resolution. New approaches to create improved optics or different acquisition modalities are required if x-ray microscopy is to make sustained contributions to such an important area of research as organic devices.