Highly anisotropic nanoscale structures are fundamentally important for understanding the properties of hybrid nanoscale systems and self-organization phenomena, but they are typically difficult to prepare experimentally. Hybrid Au and Te matchstick-like nanostructures, which display high structural anisotropy, were synthesized using small An clusters as seeds. The matchsticks were found to bean exclusive product of this reaction. We hypothesize that the mechanism of the synthesis is based on self-directed site-specific reduction of Au ions due to the gradually increasing dipole moment facilitating this process on one side of Te nanorods, which is supported by quantum mechanical calculations.