Sequence-controlled semiconducting polymers represent a new frontier in organic electronics, where precise molecular sequence directly dictates device performance. However, achieving both high sequence fidelity and structural diversity remains a significant challenge using conventional synthetic protocols. To address this issue, we introduce a versatile halide-pair-driven multicomponent polymerization (MCP) strategy that enables the library synthesis of sequence-controlled semiconducting poly(triarylamine)s (PTAAs). By optimizing halide pairing in conjunction with a rationally designed Buchwald ligand-Pd system featuring catalyst-transfer capability, we achieved efficient sequential cascade aminations, thereby enabling the MCP. The versatility of this strategy was demonstrated through the synthesis of a library of sequence-controlled PTAAs, including dendronized variants, underscoring its potential as a general platform for functional semiconducting material discovery.

Abstract Lithium (Li) metal, with its unparalleled theoretical capacity and lowest electrochemical potential, is a promising anode material for rechargeable batteries. Yet, challenges such as dendrite formation, severe electrode volume change, and ongoing Li consumption impede its practical adoption. To address these challenges, a novel approach is introduced, harnessing the switchable electrical conductivity of a nanoporous current collector for Li metal anode. A vertically aligned Nickel‐catecholate (VANC) is directly grown on the copper foil as the nanoporous current collector, and the Li intercalation and de‐intercalation of VANC reversibly decrease and increase the electrical conductivity in the direction perpendicular to the electrode, respectively. The switchable conductivity induces uniform deposition and stripping of Li metal without forming dendrite and dead Li during the Li plating/stripping process and thus enables high coulombic efficiency of over 98% even after 200 cycles. This nanoporous structure with switchable conductivity will open up a new path for reliable lithium metal anode for rechargeable battery applications.