Rationally designed, 3D-printed architectures can effectively decouple the mechanical and electrical properties of conducting polymer hydrogels.

Materials are more easily damaged during accidents that involve rapid deformation. Here, a design strategy is described for electronic materials comprised of conducting polymers that defies this orthodox property, making their extensibility and toughness dynamically adaptive to deformation rates. This counterintuitive property is achieved through a morphology of interconnected nanoscopic core–shell micelles, where the chemical interactions are stronger within the shells than the cores. As a result, the interlinked shells retain material integrity under strain, while the rate of dissociation of the cores controls the extent of micelle elongation, which is a process that adapts to deformation rates. A prototype based on polyaniline shows a 7.5‐fold increase in ultimate elongation and a 163‐fold increase in toughness when deformed at increasing rates from 2.5 to 10 000% min−1. This concept can be generalized to other conducting polymers and highly conductive composites to create “self‐protective” soft electronic materials with enhanced durability under dynamic movement or deformation.

The presence of a small amount of oligomer can induce ordering and crystallization of the parent conducting polymer, resulting in highly conductive, compositionally homogeneous crystals with defined molecular weights.

A direct template based on vertically oriented tetraaniline provides a new, general route towards vertically oriented nanopillar and nanotube arrays for a wide variety of materials. The arrays can also be patterned at micron-resolution.