Abstract The protection of Pendelikon marbles to weathering has been the main aim of numerous and longstanding studies. Latest scientific approaches in the field of conservation include methods for self-cleaning surfaces that mimic natural phenomena. In our research, we have critically studied and implemented by means of nanotechnology, the development of a biomimetic composite, protective, hybrid nanostructured film. The mineral substrates have been coated with a fluorosilanic base matrix and furthermore top-coated with a nanostructured synthesis made from amorphous silicon dioxide, sprayed using the ‘alla prima’ technique. The behaviour of the composite protective coating has been evaluated in terms of wettability, retreatability and resistance to weathering.