Topotactic ion exchange is ubiquitous in the preparation of many metastable solids with layered structures. In recent times, the scope of chimie-douce ion exchange has been extended to quasi-2D and -3D structures including nanocrystals. The low-temperature solid-state exchange is yet another unique synthetic tool to access preconceived structures for the rational design of solids. Although rational synthesis using inorganic synthons is rare, few examples exist among inorganic solids with layered structures. Herein, we extend the scope further by transforming a simple perovskite (ABO3) into a high-pressure quadruple (AA'3B4O12) perovskite. The transformation is achieved at moderate temperatures and ambient pressure via a solid-state metathesis reaction, wherein the transition metal adopts a new A-cation coordination upon exchange. Such coordination switching upon ion exchange will open up possibilities for functionality-driven structural transformations and the rational design of new solids.