Supramolecular complexation is a powerful strategy for engineering materials in bulk and at interfaces. Metal–phenolic networks (MPNs), which are assembled through supramolecular complexes, have emerged as suitable candidates for surface and particle engineering owing to their diverse properties. Herein, we examine the supramolecular dynamics of MPNs during thermal transformation processes. Changes in the local supramolecular network including enlarged pores, ordered aromatic packing, and metal relocation arise from thermal treatment in air or an inert atmosphere, enabling the engineering of metal–oxide networks (MONs) and metal–carbon networks, respectively. Furthermore, by integrating photo‐responsive motifs (i.e., TiO2) and silanization, the MONs are endowed with reversible superhydrophobic (>150°) and superhydrophilic (≈0°) properties. By highlighting the thermodynamics of MPNs and their transformation into diverse materials, this work offers a versatile pathway for advanced materials engineering. Supramolecular metal–phenolic networks, consisting of metal ions coordinated with phenolic motifs, can undergo selective thermodynamic transformations into nanoporous structures, including metal–carbon networks and metal–oxide networks, with tunable network organization and surface wettability.