Zn and Co-ZIF-4 meta-stable compounds adopt the same topology of Zeolitic imidazolate frameworks (ZIF)-4, but differ in the metal nodes (Zn versus Co). Using calorimetric and thermogravimetric analysis, here we characterized their differences in phase change processes. Upon heating, the framework of Co-ZIF-4 meta-stable crystal undergoes the crystal-to-amorphous phase transition at 590 K, which is somewhat lower than the corresponding transition previously reported in the corresponding Zn-ZIF-4. In addition, the recrystallization rate for amorphous Co-ZIF-4 is relatively higher than the corresponding one of Zn-ZIF-4. Finally, the forming Co–zni crystal begins to melt at about 824K, accompanied by quick decomposition, whereas Zn–zni undergoes complete melting which finishes at around 850K without any decomposition. Based on their differences in chemistry for Co and Zn, we elucidated the chemical origin of the discrepancies of phase transition process for Zn and Co-ZIF-4 compounds upon heating.