Homogeneous distribution of primary dendritic arm spacing (PDAS) is required to achieve uniform mechanical properties in final product of single-crystal superalloys. In this work, the dendrite characterization and orientation of Ni-based single-crystal DD6 superalloy have been deeply investigated using different methods, which include minimum spanning tree (MST), Voronoi polygon-based approach, fast Fourier transform (FFT), as well as EBSD and RO-XRD. The investigation results indicate that the mean PDAS of DD6 superalloy is about 325.7 mm and its variation ratio is 7.38%. The measured Voronoi polygon parameters suggest that the number of nearest-neighbor dendrite ranges from 5.87 to 5.93, approximating six nearest neighbors in the spatial distribution of dendrite microstructures. However, the change in ratio of six nearest number proportion has exceeded 30% for the twenty specimens. The MST method shows that the change in branch length measured from the twenty specimens achieves 26.95%. Also, the analysis results of FFT imply that the dendrite microstructures of DD6 superalloy evolve apparently. These results give the proof that the dendrite microstructures of DD6 superalloy vary with the solidified distance. Additionally, the deviation angles between preferential orientations of DD6 with the axial direction of specimen were measured by EBSD and RO-XRD, respectively. The deviation angle values of DD6 superalloy in this experiment are both within 10°. The reason for the deviation angle measured by RO-XRD being smaller is well explained due to the fact of selecting the diffraction intensity maximum angles. Furthermore, the EBSD results indicate that the orientations of DD6 superalloy prepared by grain selector can be well controlled along the Z-axial direction, but do not work in other two X and Y directions.