Nano-to-mesoscale morphology in functional organic materials play hand-in-hand with a molecule’s fundamental optical and electronic properties to govern the behavior of that material in a device. Unfortunately, such morphology and structure is particularly difficult to measure in these systems using traditional high-resolution techniques based on electrons, X-rays, and neutrons. Recently, resonant X-ray techniques have been demonstrated to provide high material contrast, identifying molecules by their unique bond structure. Not only are resonant X-rays able to quantitatively measure domain structure and composition on relevant size scales, but polarized X-rays also are sensitive to bond orientation. Our work exploring this new ability to measure molecular orientation in buried structures and interfaces has revealed just how important this orientation is in functional materials and devices such as organic solar cells and transistors. The continued development of resonant X-ray techniques to extract quantified statistical information on molecular orientation and conformation in organic structures will open new avenues to control novel properties in functional organic materials and their related devices.