Hollow spherical ZnO and hollow ZnO−Ag nanocomposites with variable percentage of loading of Ag content were successfully fabricated through a novel, template free and easily reproducible route. Extensive characterizations were carried out using FTIR, XRD, XPS, BET, TEM and SEM. The hollow morphology of the particle and the composite encouraged a detailed photocatalysis study in comparison to solid commercial ZnO and the corresponding ZnO−Ag composite. The photocatalytic activity of the hollow particle and the composite was assessed monitoring the decolouration of methylene blue dye using UV‐Vis absorption spectroscopic technique. An increased surface area for hollow morphology as compared to solid particles established a conspicuous boost in photocatalytic activity.