Through one-pot mechanochemical synthesis, a series of guests [imidazole, (aminomethyl)phosphonic acid, urea and sulfamic acid] are rapidly encapsulated into the pores of MOF NENU-3 while the MOF is formed. The synthesis of a MOF loaded with functional guests that used to take several days and require a multistep procedure can now be completed in one step within several minutes. The proton conductivities of the obtained composites increased by 2-3 orders of magnitude compared with NENU-3.