nature, which cannot meet the increasing demand for its broad applications in DSSCs. Thus, there is a huge interest in Pt-free materials for CE fabrication, such as inorganic semiconductors, [5] carbon materials, [6] conductive organic polymers, [7] and so on. [8,9] Metal-organic frameworks (MOFs) represent a class of porous coordination polymers that consist of organic ligands linker by metal ions to form crystalline assemblies, [10,11] which have been widely investigated for their attractive physical and chemical properties. [12,13] Recently, the tunable functionality of MOFs has allowed these porous materials as precursors or sacrificial templates for the preparation of electrode materials in DSSCs. [14,15] In particular, porphyrin-based MOFs (also called metal-porphyrin frameworks) [16] have been demonstrated to exhibit tunable optical, electrical, and photophysical properties, [17][18][19] which in particular suggest applications in DSSCs. However, up to now, employing metal-porphyrin frameworks for CE materials in DSSCs has not been reported.When aiming to use the potential of MOFs for electrical, electrochemical, and electronic applications, MOF thin films [20][21][22] prepared by a layer-by-layer (lbl) liquid-phase epitaxial (LPE) procedure have attracted huge interest. These surfacemounted MOFs or SURMOFs are assembled by a sequence of simple immersion processes, subsequently into solution of the metal source and the organic ligand. They exhibit a number of interesting properties, including controllable thickness, crystallinity, high degree of orientation, and homogeneous surface. So far, the lbl-approach has been successfully used to realize several types of SURMOFs, [23] e.g., HKUST-1 (Cu 3 (BTC) 2 , BTC = benzene-1,3,5-tri-carboxylate), SURMOF-2, Zn(2-methylimidazolate) 2 (ZIF-8), etc. [23][24][25] These SUR-MOFs are epitaxially grown on appropriately functionalized substrates by coordination bonding between metal ions and organic ligands. The growth of SURMOFs based on lbl protocols involving noncovalent interactions (such as van der Waals, hydrogen bonding, and other weak interactions, etc.) has not yet been studied. When using porphyrinic ligands, such SUR-MOFs are expected to have interesting applications in catalysis, electronic devices, and in photovoltaics. [26][27][28][29][30][31][32][33][34] Herein, we report a layer-by-layer epitaxial growth strategy for preparing SURMOFs with a layered structure. 2D sheets consisting of paddle-wheel (PW) units linked by porphyrin linkers are stacked by the interaction between layers being of van der Waals type. X-ray diffraction (XRD) data reveal that layer-by-layer deposition on appropriately functionalized substrates yields In this work, monolithic, crystalline, porous, and oriented porphyrin thin films are grown using a novel van der Waals layer-by-layer (lbl) epitaxial growth protocol, yielding an unusual AB-stacking motif of these interesting macrocycles units. Subsequently, these surface-mounted metal-organic frameworks (SURMOFs) are transformed by th...