Abstract Exfoliation of layered materials is a key to obtaining high‐performance 2D nanomaterials. Rapid and inexpensive exfoliation methods of the layered materials have been proposed recently. Along with the development, high‐throughput dimensional evaluation methods for the 2D nanomaterials are required as well. A novel method of dimensional evaluation for 2D nanomaterials is evolved. That can be characterized by utilization of synchrotron X‐ray powder diffraction. A bulky amount of hexagonal boron nitride (h‐BN) particles in solvents via wet jet milling is exfoliated and h‐BN 2D nanomaterials in plenty is obtained. Employing the resultant h‐BN 2D nanomaterials as measurement specimens, validity of the dimensional evaluation method is verified. With the powerful characterization method at hand, it is expected that optimization of various exfoliation processes will flourish in the near term.