The nanoscale dynamical processes of organization, complexing, and aggregation of biomolecules lie at the foundation of many critical processes in metabolism, signaling, and disease. Our understanding of these processes, particularly those occurring in crowded environments, remains limited thus far by our inability to probe small aqueous volumes optically. To generate a nanoscale optical probe for visualizing nanoscale biological dynamics, we have developed and demonstrated a new approach that combines the advantages of electron and fluorescence microscopies, namely the nanoscale focusing and fast scanning capabilities of electron microscopy and the chemical specificity and non-invasiveness of fluorescence microscopy. Our new super resolution optical imaging platform consists of a high-brightness, rapidly scannable, 20-nm optical spot in cathodoluminescent (CL) thin film generated by a low energy, tightly focused electron beam from a scanning electron microscope (SEM). Because the CL film is only 10-20 nm thick, optical excitations activated by the electron beam in the CL film can be non-radiatively transferred to adjacent fluorescently labeled molecules in an encapsulated sample volume via Forster resonance energy transfer (FRET). By correlating the position of the electron beam with fluorescence from the sample, we can generate images with nanoscale resolution, high optical contrast, and fast acquisition rates. Using this approach, we have successfully imaged plasmonic metal nanoparticles with 46 nm-resolution and demonstrated high-resolution CL-activated FRET with luminescent polymer blends. By encapsulating a aqueous biological sample adjacent to the film, we anticipate imaging processes, such as DNA repair, protein aggregation, and diffusion of protein complexes on lipid membranes. We aim to achieve a spectrally-specific scanning optical microscopy with at least 20 nm lateral resolution and 10 nm axial resolution with a fast acquisition rate.