Although great progress has been made in the design, synthesis, and performance expansion of porous materials, new porous materials with stable structures still need to be explored further. In recent years, porous molecular crystals formed by intermolecular interactions have attracted wide attention from chemists, especially metal hydrogen-bonded organic frameworks (M-HOFs) formed by connecting metal complexes through hydrogen bonds. Metal complexes with specific properties (e.g., magnetism, luminescence, sensing, and catalysis) can expand and develop the application of M-HOFs further. However, the huge volume, irregular shape, complex coordination modes, and interference of coordination bonds pose certain challenges in the synthesis and performance expansion of M-HOFs. In this frontier, we summarize the latest progress in the use of 3d, 4d, and 4f metal complexes for the synthesis of M-HOFs, and briefly introduce the performance expansion of these M-HOFs, which is expected to help expand new porous materials with stable structures and specific functions.