AbstractRecently, four-dimensional (4D) functional nano-materials have attracted considerable attention due to their impact in cutting-edge fields such as nano-(opto)electronics, -biotechnology or -biomedicine. Prominent optical functionalizations, representing the fourth dimension, require precisely tailored light fields for its optimal implementation. These fields need to be like-wise 4D, i.e., nano-structured in three-dimensional (3D) space while polarization embeds additional longitudinal components. Though a couple of approaches to realize 4D fields have been suggested, their breakthrough is impeded by a lack of appropriate analysis techniques. Combining molecular self-assembly, i.e., nano-chemistry, and nano-optics, we propose a polarization nano-tomography of respective fields using the functional material itself as a sensor. Our method allows a single-shot identification of non-paraxial light fields at nano-scale resolution without any data post-processing. We prove its functionality numerically and experimentally, elucidating its amplitude, phase and 3D polarization sensitivity. We analyze non-paraxial field properties, demonstrating our method’s capability and potential for next generation 4D materials.