Semiconductor nanowires (NWs) are considered the ideal building blocks for future nanodevices. [1] In particular, because of their 1D geometry, NWs have attracted tremendous attention due to their potential applications in waveguides, [2] nanolasers, [3] photodetectors (PDs), [4] and field-effect transistors. [5] Although great progress has been made in the synthesis of semiconductor NWs, most of the reported wires were grown with random orientations, which restrained their application in high-density integrated circuits. [6] Generally, practical utilization at the circuit level requires the large-area horizontal alignment of semiconductor NWs with a controlled orientation on a substrate. Several techniques, such as optical tweezers, [7] micromanipulation, [8] and Langmuir-Blodgett assembly [9] may align NWs in well-organized arrays. However, these postgrowth assembly strategies are still subject to poor controllability, low throughput, and high cost, which prevents their application in scale production. [3a,10] The direct epitaxy of semiconductor NWs on an appropriate substrate has great potential to efficiently produce macroscopic-scale wire arrays with horizontal alignment through combining the growth and assembly of NWs into one step. The guided growth of laterally aligned NWs has been successfully achieved for InP NWs on germanium, [11] GaAs NWs on GaAs (100) substrates, [12] GaN and ZnSe NWs on sapphire, [10a,13] etc. These covalent hetero-or homoepitaxies strictly require the substrates and the corresponding epitaxial NWs to have similar crystalline symmetries, lattice parameters, and thermal expansion coefficients to avoid large interface strain. Moreover, the chemical covalent bonds formed between epitaxial NWs and substrates make wire arrays difficult to be peeled off from the grown substrates. This prevents the wires from further being transferred onto other substrates for various functional device applications. Mica, a typical layer-structured mineral, can act as an ideal deposition substrate interacting with the epitaxial wires by the van der Waals (vdW) force, due to its danglingbond-free and atomically smooth surface. [14] The weak vdW force dominated incommensurate epitaxy of wires horizontally on vdW substrates may tolerate a large lattice mismatch, while the wires may still maintain a definite in-plane direction relative to the substrate to minimize the system energy. [15] In addition, the weak interacting force between the epitaxial wire and mica facilitates the transfer of the grown wire arrays without any corrosive reagents etching the substrate, but with the assistance of water. [16] Although mica has been extensively used as a vdW epitaxial substrate for the growth of vertically aligned semiconductor wires and 2D materials, [16,17] the growth of horizontally aligned semiconductor wires on mica is only limited to the material systems of WO 3 , Pb 1Àx Sn x Se, and all inorganic perovskites. [18]