UiO−66−NH2 is a typical Zr−based metal-organic frameworks (Zr−MOFs) with considerable application prospect in CO2adsorption. It is a good filler combined with polyvinylamine (PVAm) to prepare mixed-matrix membranes (MMMs). However,the scalingeffect of UiO−66−NH2 preparation is too obvious to scale it up to more than ten-gram-scale. A series of UiO−66−NH2 was synthesized bychanging the ratio of water-acetic acid. Scanning Electron Microscope (SEM),X−ray Diffraction (XRD),Fourier Transform Infrared (FT-IR) and BET test were used to characterize the samples. Through the analysis of characterization results,a mechanism for water-acetic acidpromotion of Zr−MOFs secondary-building-unit (SBU) formation was proposed,which has guided the hundred-gram-scale synthesis ofUiO−66−NH2 particles. Furthermore, these particles were combined with polyvinylamine (PVAm) to prepare UiO−66−NH2/PVAmMMMs, whose separation performance were tested using simulated flus gas (volume fractions of CO2 and N2 are 15% and 85%,separately). Compared with PVAm membranes,the separation performance of MMMs increases. The CO2 permeance reaches 1 937 GPUand the CO2/N2 separation factor reaches 85. The result of the cost estimation shows that the use of MMMs can effectively reduce the cost of carbon capture and it also has application prospects in flus gas carbon capture.