A hybrid montmorillonite (MMT)/reduced graphene oxide (rGO) film was realised and used as a non-invasive sensor for the monitoring of water absorption and desorption in pristine and consolidated tuff stones. This film was obtained by casting from a water dispersion containing graphene oxide (GO), montmorillonite and ascorbic acid; then the GO component was thermo-chemically reduced and the ascorbic acid phase was removed by washing. The hybrid film showed electrical surface conductivity that varied linearly with the relative humidity, ranging from 2.3 × 10−3 S in dry conditions to 5.0 × 10−3 S at 100% RH. The sensor was applied onto tuff stone samples through the use of a high amorphous polyvinyl alcohol layer (HAVOH) adhesive, which guaranteed good water diffusion from the stone to the film and was tested during water capillary absorption and drying tests. Results show that the sensor is able to monitor water content changes in the stone, being potentially useful to evaluate the water absorption and desorption behaviour of porous samples both in laboratory environments and in situ.