The lateral alignment of {012} habit-modified calcite crystals with respect to a carboxylic acid terminated self-assembled monolayer (SAM) of thiols has been determined. The crystals were grown from a Kitano solution (pH 5.6-6.0), and the samples were investigated with scanning electron microscopy, X-ray diffraction, and polarization microscopy. For the first time, a lattice match in one direction, which is the nearest neighbor direction of the SAM and the calcite (100) direction, has been experimentally shown. The experimental results are in good agreement with the theoretical models proposed in previous work, and it is expected that this method can be applied to similar systems where inorganic crystals nucleate with a preferred orientation to a SAM.