ConspectusThe significance of the new synthetic approach is that it can overcome the limitations of conventional methods and produce previously inaccessible polymer structures and materials. The solid-phase synthesis developed by Merrifield in 1964 is widely employed for the synthesis of biological molecules, such as peptides, nucleic acids, and oligosaccharides. Although the variety of iterative reactions available is theoretically implemented for most organic synthesis protocols, they are usually required to have high efficiency against sluggish reaction kinetics at the solid-liquid interface and process with protection and deprotection steps. Generally, unsatisfied reaction dynamics at the solid-liquid interface cannot statistically permit accurate and uniform polymer synthesis of sophisticated structures and functions within an acceptable time scale. To address this challenge, we propose the concept of solid-phase electrosynthesis, which simultaneously enables rapidly surface-initiated uniform electrosynthesis and unidirectional assembly of metallopolymers via kinetically accelerated and statistically allowed iterative growth. In particular, on a self-assembled monolayer (SAM) of the metal complex with electroactive unit A, the iterative monomer with two electroactive units A and B can be alternatively activated by oxidative and reductive potentials for A-A and B-B covalent couplings with the SAM, respectively. This enables topochemical one-by-one additions of the iterative monomers to end-on-oriented self-assembled molecules through alternative redox reactions. Each iterative step is purified by washing. Repeating the same iterative reaction enables further reaction of the unreactive sites on the SAMs and repairs the morphology defects, thereby ensuring the statistically allowed uniform synthesis and fabrication of polymer monolayers. The resulting monolayers exhibit subnanometer-uniform morphology over centimeter-sized areas with crystalline states and show thicknesses similar to theoretical molecular lengths. This demonstrates the unidirectional formation of polymer assemblies, providing a pathway for obtaining highly ordered formation of noncrystalline polymers. The length-controlled electrosynthesis of metallopolymers can be generalized for many types of organic ligands and metal species, enabling quantitative design of the composition and sequence-controlled metallopolymers with the precise relationships of structures and properties. Solid-phase electrosynthesis offers a unique approach to synthesize polymer structures and monolayers with enhanced functionality and superior physical properties, including physical density, modulus, and conductance. Through the utilization of precise and efficient iterative growth, this predictable electrosynthesis, coupled with optical and electrical monitoring, not only expands the scope of current synthetic chemistry but also paves a potential way for the automated generation of optoelectric molecular monolayers with large-area dimensional consistency and enhanced physical performance.