We use solid-state 27Al NMR spectroscopy to test four aluminum-based metal–organic framework (MOF) materials—ICR-2, ICR-4, ICR-6, and ICR-7—against their structural models obtained from electron and X-ray diffraction. The lineshape analysis of the 27Al NMR spectra reveals varying degrees of disorders in the Al coordination environment, depending on the sample, which we were able to parameterize in terms of the extended Czjzek model (ECM) of the electric field gradient (EFG) distribution. The model’s degree-of-disorder parameter ε was found to correlate inversely with the crystallite size of the MOFs. This suggests that the EFG distribution is related to a high surface-to-volume ratio of the particles and can be ascribed to the deviation of molecular arrangements near the surface from the bulk crystalline order. The ECM’s parameters for a fixed part of the EFG tensor, a quadrupolar coupling constant CQ,0 and asymmetry parameter η0, were compared to the EFG parameters calculated on fully periodic models using density functional theory (DFT). The DFT-calculated CQ was found to exceed CQ,0 by 25–60%, depending on the MOF. Although this result finds support in the literature, an explanation of such apparent spectral narrowing is still lacking.