A layered prism is an ideal system for fundamental studies due to its unique structure with uniform sized sheets. However, there are very limited reports in the last few decades on the preparation of such materials. In this contribution, we report for the first time the preparation of alpha-ZrP intercalation compound-based hexagonal prisms. Preferential crystal growth perpendicular to the (001) crystal plane of alpha-ZrP intercalation compounds was achieved by incorporating a complexing agent and a layer growth coordinator into a crystal growth reaction system. With the presence of a layer growth coordinator to coordinate the crystal growth perpendicular to the (001) crystal plane and the presence of a complexing agent to slow down the crystal growth rate, the previously unknown layer growth coordination effect is revealed. After a facile ion exchange treatment, pure alpha-ZrP hexagonal prisms can also be obtained.