We use molecular dynamics simulations to investigate the nucleation of calcite crystals on self-assembled monolayers. We show how the presence of bicarbonate ions adsorbed on the monolayer surface can both aid nucleation and control the orientation of the growth of the crystal. Using a simple model of the nucleation process and calculated interfacial energies, we calculate the enhancement (with respect to the homogeneous nucleation rate) of the nucleation of calcite on the (0112) and (0001) faces. The calculations show clearly that the (0112) face is favored over the (0001) face and that the nucleation rate is enhanced for self-assembled monolayers made from molecules containing an even number of carbon atoms in the alkyl chain over those containing an odd number.