Fluorescence microscopy is an essential analytical tool in the biomedical laboratory to investigate cells and tissues. Diffraction, however, limits the resolution of this imaging technique to the submicron scale. As a result, the factors regulating biological processes and structures at the molecular level cannot be appreciated with conventional fluorescence microscopy. The photoswitchable luminescent probes offer the opportunity to overcome this limitation and permit the visualization of biological samples with a resolution at the nanoscale. Thus, our review article highlights some advanced organic molecules that can be utilized as invaluable molecular probes for super-resolution imaging and have a significant long-term impact on biomedical research in addition to other promising applications such as colorimetric identification of cyanide, photoactivatable barcodes, and saving papers with switchable ink.