New ambient temperature liquid calcium alkoxides, [Ca(O(CH₂CH₂O)₃CH₃)₂] (1) and [Ca(O(CH₂CH₂O)₃CH₂CH₃)₂] (2), together with [Ca(OCH₂C(CH₃)₃)₂] (3), were synthesised by reaction of ammonia-activated calcium with the appropriate alcohol. Their potentiality as stone consolidant products was investigated and compared with those of other alkoxides: [Ca(OCH₂CH₃)₂(CH₃CH₂OH)₄] (4), [Ca(OCH₃)₂] (5), [{Ca(OCH₂CH₂OCH₃)₂}₉] (6), already described in the literature. Reaction of 1–3 with the atmosphere was studied, final products analysed and kinetic pathways investigated. The reaction produces CaCO₃ and the vaterite/calcite ratios observed in the coatings generated from isopropyl alcohol solutions of 1–6 were found to considerably vary with the alkoxide precursor, which has a strong influence also on the morphology of the produced films. Furthermore, their efficiency as stone consolidants was tested by ultrasound measurements.