Calcium carbonate was preferentially electrodeposited onto the relatively high pH surface of an iron electrode held at highly reducing potentials in a CaCl2+NaHCO3 solution. Solution composition, temperature and additives influenced the structure and composition of the calcium carbonate deposit. The conditions that produce the three major crystalline phases (aragonite, vaterite and calcite) along with unstructured phases of calcium carbonate have been identified with FTIR spectroscopy. The use of Raman spectroscopy was also investigated as an in situ detection method for monitoring the calcium carbonate deposition process. The results demonstrate the applicability of an electrochemical method for producing controlled calcium carbonate deposition from solution.