Nano-and micrometer-sized colloidal particles (CPs) with shape anisotropy (e.g., rod-shaped particles) and chemical heterogeneity (e.g., patchy particles) have attracted significant attention owing to their fascinating optical, electronic, and magnetic properties in materials sciences. [1][2][3] Self-assembly of such colloidal building blocks as "atoms" or "molecules" (so-called "colloidal molecules") into novel architectures or ordered ensembles provides new opportunities for engineering materials and devices with otherwise unattainable properties. [4,5] In particular, assembly of rodlike CPs with two or multiple blocks can potentially produce a variety of spectacular structures, which arise from the interplay and competition of the structural asymmetry of rods, the orientation, and phase segregation of blocks. [1a, 6] Currently, the preparation of such segmented rodlike CPs mainly relies on templated electrochemical deposition, [7] galvanic replacement, [8] phase separation, [3f] chemical vapor deposition, [9] hot coordinating solvents method, [10] and cation-exchange reactions. [11] These approaches, however, are either limited to crystalline or conductive materials, or they require the use of templates. The synthesis of segmented rodlike particles from amorphous materials (e.g., SiO 2 ) still remains a challenge.From the study of the assembly of colloidal molecules one can fundamentally learn and understand the general principles of atomic and molecular interactions using CPs as model systems, [1,12] and one can practically use the strategy known from the self-assembly of atoms or molecules as an inspiration for the design of new functional materials of CPs, such as nonconventional photonic crystals. [3d, 13] Anisotropic rodlike CPs with hydrophilic and hydrophobic blocks are typical models for the investigation of assembly behaviors and molecular interactions of amphiphilic molecules (AMs). [8] The Mirkin group reported an inspiring example of template-directed assembly of two-segment gold-polypyrrole (Au-PPy) rods prepared by a templating method. [7a] The assembly of Au-PPy rods is driven by a delicate balance of [*] Dr.