Although some COF structures can be precisely identified by single crystal X-Ray diffraction . However, the great challenge in the synthesis of the COF single crystal, especially LCOFs, renders the revealing of most of the COFs crystal structure still heavily depends on the powder XRD together with the theoretical simulation. There is no unambiguous knowledge of the atomistic LCOF structures as powder X-ray diffraction (PXRD) data itself does not contain sufficient information to resolve the structure in atomistic resolution, and predicted structures do not closely match experimental PXRD patterns. LCOF PXRD patterns commonly have signs of structural disorder with wide, diffused peaks, while those simulated from predicted structures feature many narrow peaks (Figure ). Recently, a total scattering study by Pütz et al. has shown that LCOFs with a well-defined local structure exhibit a long-range stacking disorder. This disorder systematically causes false interpretation of experimental results, which commonly is mapped to an average structure of high symmetry in stacking direction. Similar disorder was identified layered zeolites and molecular crystals. Here, we present a general approach to simulate the crystal disorder in LCOFs, by statistically stacking COF monolayers in a sequence following a Maxwell-Boltzmann distribution of their relative stacking energies. This model yields unprecedented agreement of PXRD patterns between experiment and theory, to the point of being able to identify the actual ratios of stacking modes present in the samples.