Single crystal CrN/ScN superlattice films with modulation periods of 1.64 nm were grown on MgO(001) substrates. By utilizing a magnetically enhanced plasma in the vicinity of the substrate and a negative substrate bias, ion/metal nitride flux ratios of 45 and 144 were achieved during deposition of CrN and ScN, respectively. The effects of ion energies in the range [16–58 eV] and substrate temperatures in the range [535–853 °C] on the composition, interface width, crystal quality, and microstructure evolution were investigated using elastic recoil detection analysis, hard X-ray reflectivity, X-ray diffraction, and transmission electron microscopy (TEM). Minimal interface widths of 0.2 nm = 1/2 nitride unit cell were achieved at a growth temperature of 735 °C and ion energies of 24 and 28 eV for CrN and ScN, respectively. Under these conditions, also an optimum in the crystal quality was observed for near stoichiometric composition of CrN and ScN. TEM confirmed a cube-on-cube epitaxial relationship for the system with CrN(001) ScN(001) MgO(001) and CrN[100] ScN[100] MgO[100]. Also, the layers were coherently strained to each other with no misfit dislocations, threading dislocations, surface cusps, voids or gas bubbles present. Higher ion energies or lower deposition temperatures gave over-stoichiometric films with poor superlattice modulation while higher growth temperatures yielded a decreased crystal quality, due to loss of N. As-deposited superlattices with only 61 periods exhibited an absolute soft X-ray reflectance of 6.95% at an energy of 398.8 eV (Sc 2p-absorption edge) which is comparable to the performance of Cr/Sc. The compositional modulation and phase structure was stable during extended annealing at 850 °C, which is the highest thermal stability for an X-ray multilayer mirror. It is concluded that the ScN layers serve as effective diffusion barriers to hinder decomposition of the CrN layers and stabilize the pseudomorphic superlattice structure. Nanoindentation experiments showed that the hardness of the CrN/ScN superlattice films was 19 GPa.