Zinc oxide (ZnO) in various nano forms (nanoparticles, nanorods, nanosheets, nanowires and nanoflowers) has received remarkable attention worldwide for its functional diversity in different fields i.e., paints, cosmetics, coatings, rubber and composites. The purpose of this article is to investigate the role of photocatalytic activity (role of photogenerated radical scavengers) of nano ZnO (nZnO) for the surface activation of polymeric natural fibres especially cotton and their combined effect in photocatalytic applications. Photocatalytic behaviour is a crucial property that enables nZnO as a potential and competitive candidate for commercial applications. The confirmed features of nZnO were characterised by different analytical tools, i.e., scanning electron microscopy (SEM), field emission SEM (FESEM) and elemental detection spectroscopy (EDX). These techniques confirm the size, morphology, structure, crystallinity, shape and dimensions of nZnO. The morphology and size play a crucial role in surface activation of polymeric fibres. In addition, synthesis methods, variables and some of the critical aspects of nZnO that significantly affect the photocatalytic activity are also discussed in detail. This paper delineates a vivid picture to new comers about the significance of nZnO in photocatalytic applications.