The relationship between orientation distribution functions (ODFs) from advanced dMRI and the real tissue microstructure is under active research. We utilized three-dimensional (3D) serial block-face scanning electron microscopy in the corpus callosum and cingulum, and implemented 3D structure tensor (ST) analysis to produce ODFs comparable to dMRI ODFs from the same locations. The ODFs were parametrized using Watson distribution. Our results showed a clear correspondence in orientation estimates, but dispersion estimates were not as clearly correlated. ST analysis combined with 3D SBEM has great potential to unveil the complexity of the underlying microstructure in biological tissues.