The structure of microcontact-printed self-assembled monolayers is significant for a number of technological applications as well as for a fundamental understanding of the self-assembly process. The structural differences between printed and solution-deposited monolayers of alkanethiol on Au(111) have been examined utilizing grazing incidence X-ray diffraction and atomic force microscopy. Although the local structures are found to be similar, the domain structure and therefore macroscopic packing of the molecules are found to vary. Surprisingly, printed decanethiol monolayers appear to be significantly better ordered translationally than those formed by standard solution techniques.