When films were directly deposited on SiO2/Si without a graphene layer (Figure ) under identical growth conditions, a relatively weak scattering without a preferred orientation was observed (Figure ). This underscores the essential role of graphene in the preferential growth of the UiO-66-NH2 films. Moreover, substrates featuring only a graphene layer on SiO2/Si displayed no detectable signals (Figure ) confirming that the observed signals in the thin films originate from UiO-66-NH2. Further analysis of 1D scattering profiles, achieved by integrating the full scattering signal through GIWAXS (Figure ), agreed well with the simulated powder pattern of UiO-66-NH2. To elucidate the influence of graphene on the preferred orientation of UiO-66-NH2, the selected area electron diffraction (SAED, Figure ) was carried out to investigate the potential lattice registry between UiO-66-NH2 and graphene. Analysis revealed that UiO-66-NH2 film oriented along a-out-of-plane direction has only a small lattice mismatch with graphene, -3.04% along the b-axis and 5.26% along the c-axis (Figure , Supplementary note 7). This analysis utilized the smallest structural unit of UiO-66-NH2 to fit on the graphene lattice, suggesting graphene offers the structural registry in facilitating the preferred growth orientation along 200 lattice plane of UiO-66-NH2.