Layered double hydroxides (LDHs) can play an important role in various areas, but conventional LDHs synthesis often causes product agglomeration and generates plenty of high-salt wastewater, and requires a time-consuming aging process to reach the desired purity and crystalline state. Herein, we report the synthesis of MgAl-LDH, a representative of these kinds of ionic lamellar inorganic solids, with a novel method involving the reaction of magnesium oxide (MgO) with aluminate ions (Al(OH)4-) in a strongly alkaline environment. The formation of MgAl-LDH follows a mechanism of interfacial dissolution-reprecipitation (IDR), i.e., Mg2+ ions released at the interface of dissolved MgO react immediately with Al(OH)4- ions to reprecipitate as MgAl-LDH. The obtained MgAl-LDH has no impurity phases and shows high crystallinity, high specific surface area, and a narrow particle size distribution. Moreover, MgAl-LDH is intercalated with OH- anions, so it can be directly used as a Brønsted base catalyst and ion exchanger. The novel method requires no time-consuming aging process and is highly scalable. It is also shown that a closed-loop synthesis of MgAl-LDH without waste discharge can be achieved with an appropriate Al source, e.g., Al(OH)3, and a recycled NaOH solution.