A high-performance semiconductor zinc oxide (ZnO) on melamine formaldehyde-coated cellulose nanocrystals (MFCNCs) was synthesized and evaluated for its application in smart cosmetics. These ZnO@MFCNC hybrid nanostructures were evaluated for their in vitro sun protection factor performance and photocatalytic activity under simulated UV and solar radiation. The photodegradation kinetics of a model pigment (methylene blue) was fitted to the Langmuir-Hinshelwood model. A 4-fold increase in the photocatalytic activity of ZnO@MFCNCs was observed when compared to pure ZnO. This is associated with (i) increased specific surface area provided by the MFCNC template, (ii) confined surface energy and controlled growth of ZnO nanoparticles, and (iii) entrapment of photoinduced charge carriers in the pores of the core-shell MFCNC rod, followed by fast promotion of interfacial e-charge transfer to the surface of the catalyst. The present study demonstrates how an increase in photocatalytic activity can be engineered without the introduction of structural defects or band gap tailoring of the semiconductor. The aqueous-based ZnO@MFCNC hybrid system displayed attractive UV-absorption and photocatalytic characteristics, offering the conversion of this renewable and sustainable technology into intelligent cosmetic formulations.