Molecular dynamics (MD) simulations were used to explore adsorption on calcite, from a 1:1 mixture of ethanol and water, on planar {10.4} and stepped, i.e. vicinal, surfaces. Varying the surface geometry resulted in different adsorption patterns, which would directly influence the ability of ethanol to control calcite crystal growth, dissolution, and adsorption/desorption of other ions and molecules. Ethanol forms a well-ordered adsorbed layer on planar faces and on larger terraces, such as between steps and defects, providing little chance for water, with its weaker attachment, to displace it. However, on surfaces with steps, adsorption affinity depends on the length of the terraces between the steps. Long terraces allow ethanol to form a well-ordered, hydrophobic layer, but when step density is high, ethanol adsorption is less ordered, allowing water to associate at and near the steps and even displacing pre-existing ethanol. Water adsorbed at steps forms mass transport pathways between the bulk solution and the solid surface. Our simulations confirm the growth inhibiting properties of ethanol, also explaining how certain crystal faces are more stabilized because of their surface geometry. The -O(H) functional group on ethanol forms tight bonds with calcite; the nonpolar, -CH3 ends, which point away from the surface, create a hydrophobic layer that changes surface charge, thus wettability, and partly protects calcite from precipitation and dissolution. These tricks could easily be adopted by biomineralizing organisms, allowing them to turn on and off crystal growth. They undoubtedly also play a role in the wetting properties of mineral surfaces in commercial CaCO3 manufacture, oil production, and contamination remediation.