Rock-based materials exposed to outdoor environments are naturally colonised by an array of microorganisms, which can cause dissolution and fracturing of the natural stone. Biocolonisation of monuments and architectures of important cultural heritage therefore represents an expensive and recurring problem for local authorities and private owners alike. In this area, preventive strategies to mitigate biocolonisation are generally preferred to curative approaches, such as mechanical cleaning by brush or high-pressure cleaning, to remove pre-existing patina. The aim of this work was to study the interaction between biocidal polyoxometalate-ionic liquid (POM-IL) coatings and calcareous stones and evaluate the capacity of these coatings to prevent biocolonisation through a series of accelerated ageing studies in climate chambers, carried out in parallel with a two-year period of outdoor exposure in north-eastern France. Our experiments show that POM-IL coatings did not affect water vapour transfer nor significantly alter the total porosity of the calcareous stones. Simulated weathering studies replicating harsh (hot and wet) climatic weather conditions demonstrated that the colour variation of POM-IL-coated stones did not vary significantly with respect to the natural uncoated stones. Accelerated biocolonisation studies performed on the weathered POM-IL-coated stones proved that the coatings were still capable of preventing colonisation by an algal biofilm. However, a combination of colour measurements, chlorophyll fluorescence data, and scanning electron microscopy imaging of stones aged outdoors in northern France for two years showed that coated and uncoated stone samples showed signs of colonisation by fungal mycelium and phototrophs. Altogether, our results demonstrate that POM-ILs are suitable as preventative biocidal coatings for calcareous stones, but the correct concentrations must be chosen to achieve a balance between porosity of the stone, the resulting colour variation and the desired duration of the biocidal effect over longer periods of time, particularly in outdoor environments.