The challenge of correlating a material's structure to its functional properties is a cornerstone issue 35 in material sciences. Unlocking this structure-function relationship is crucial for rational design, ultimately leading to improved properties and efficiencies. Existing characterization methods often singularly focus on either a material's structure or its properties. Even imaging techniques fall into the categories of structural or functional imaging, where the latter directly probes the material's properties and functions. Comprehensive understanding necessitates applying multiple methods to a single sample, complicating the characterization process. Techniques like scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD) may alter material properties due to their operational requirements. In contrast, lightbased methods such as absorption, photoluminescence (PL) microscopy, and spectroscopy are non-invasive but suffer from limited resolution. Super-resolution microscopy techniques using luminescence have been impactful in fields such as biology and material sciences. However, due to the high chromophore density and the spatial mobility of emitting excited states in solid functional materials, most super -resolution methods fail to provide the structural insights they promise. Hence, super-resolution in material sciences is mostly used on individual, well-separated objects such as (conjugated) polymers , j-aggregates or individual nano/microcrystals. Consequently, SEM remains the preferred tool for structural characterization of luminescent materials, but it is not applicable when materials are integrated into multilayered optoelectronic devices. While combining SEM with PL measurement to connect the photo physics with the morphology is possible, it is challenging. Analyzing these devices during operation necessitates non-invasive techniques that can penetrate through layers and concurrently assess morphology and optoelectronic properties.