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This study refers to the application of in-situ electrochemical synthesis as an alternative method to improve the properties of porous materials against harmful external agents that deteriorate them. It is oriented to an understanding of the effects of crystallisation on the pore structure of different compounds commonly used in the restoration and conservation of porous materials (historical ceramics, building walls, sculptures, or biomedical applications). It analyses the microstructural, chemical details, and stability of the neo-formed phases that modify the pore network. The electrochemical synthesis was carried out at ambient temperature (20 °C), over high porous sandstone for crystallising Ca carbonate, Mg carbonate, Ca phosphate, and Ca oxalate compounds. Based on the neo-formed minerals, a comparison was made depending on their specific properties defining how they affected the pore structure. The characterisation included polarised light optical microscopy, environmental and field-emission scanning electron microscopy, digital image analysis, cathodoluminescence (CL-ESEM),energy-dispersive X-ray spectroscopy, and X-ray microdiffraction. Aragonite, hydromagnesite, hydroxyapatite, and whewellite were identified as the majority phases depending on the treatment. Phase transformation, dehydration, and dissolution-re-precipitation processes suggested different degrees of stability, including aragonite/calcite (CaCO3 treatment) and hydromagnesite/magnesite (MgCO3 treatment) transformations and simultaneous crystallisation of brushite/hydroxyapatite ((Ca3(PO4)2 treatment). Electrocrystallisation induced changes in inter-granular porosity, the development of secondary porosity inherent to the minerals, and differences in pore cementation depending on its mineralogy. Among the treatments, Mg carbonate reduced porosity most effectively, followed in descending order by calcium carbonate and calcium phosphate, being the calcium oxalate the less effective.