Structural characterization and strain measurements were conducted on Mo/Ni multilayers, with bilayer periods between 10 Å and 200 Å, utilizing symmetric, asymmetrin, and grazing incidence x-ray diffraction techniques. The structural difference between the 15 Å and 20 Å modulation wavelength samples, evident in the symmetric high angle diffraction spectra, is attributed to the absence of crystalline registry in the early stages of sputter deposition, yielding crystalline order only when the bilayer deposition thickness exceeded 15 Å. The dominant mechanism for the observed modulation wavelength dependent strain behavior, both in the growth direction and in the plane of the film, is consistent with a coherency strain model. The orientation relationship predicted for the Mo/Ni system, based on their atomic radii ratio is the Nishiyama-Wasserman relationship, (110)BCC//(111)FCCandBCC//FCC. This relationship would provide the source for the observed coherency strain.