Diarylethenes (DAE), a class of best performing photoswitchable compounds, where the key features of stability, photoisomerization wavelengths, quantum yield and variability in the photoisomers significantly depend on their derivatization. The last decade has witnessed a surge in the engagement of DAEs to different areas of chemical and biological impacts like catalysis in synthetic organic chemistry, biological markers for in vivo imaging of live cells, chemosensing within cells to photo-dynamic therapy by controlled generation of singlet oxygen. Previous reviews on applications of DAE-based systems did not predominantly cover all the aspects of biological and industrial implementations. They have covered only one field of application either in the biological science or the synthetic aspect or photochromic aspects only. This review is a coalition of all those aspects in last six years. Here the variation of properties of the DAE systems with respect to structural diversifications have been discussed in detail along with their potential applications in catalysis, regulating singlet oxygen generation, photodynamic therapy, bioimaging and their future prospects. We hope that this review will certainly motivate researchers to generate new DAE architectures with superior bioimaging or catalyzing properties in future.