Elastomers with high dielectric permittivity that self‐heal after electric breakdown and mechanical damage are important in the emerging field of artificial muscles. Here, a one‐step process toward self‐healable, silicone‐based elastomers with large and tunable permittivity is reported. Anionic ring‐opening polymerization of cyanopropyl‐substituted cyclic siloxanes yields elastomers with polar side chains. The equilibrated product is composed of networks, linear chains, and cyclic compounds. The ratio between the components varies with temperature and allows realizing materials with largely different properties. The silanolate end groups remain active, which is the key to self‐healing. Elastomeric behavior is observed at room temperature, while viscous flow dominates at higher temperatures (typically 80 °C). The elasticity is essential for reversible actuation and the thermoreversible softening allows for self‐healing and recycling. The dielectric permittivity can be increased to a maximum value of 18.1 by varying the polar group content. Single‐layer actuators show 3.8% lateral actuation at 5.2 V µm –1 and self‐repair after a breakdown, while damaged ones can be recycled integrally. Stack actuators reach an actuation strain of 5.4 ± 0.2% at electric fields as low as 3.2 V µm –1 and are therefore promising for applications as artificial muscles in soft robotics.

Stretchable electrodes are more suitable for dielectric elastomer transducers (DET) the closer the mechanical characteristics of the electrodes and elastomer are. Here, a solvent-free synthesis and processing of conductive composites with excellent electrical and mechanical properties for transducers are presented. The composites are prepared by in situ polymerization of cyclosiloxane monomers in the presence of graphene nanoplatelets. The low viscosity of the monomer allows for easy dispersion of the filler, eliminating the need for a solvent. After the polymerization, a cross-linking agent is added at room temperature, the composite is solvent-free screen-printed, and the cross-linking reaction is initiated by heating. The best material shows conductivity 𝝈 = 8.2 S cm -1 , Young's modulus Y 10% = 167 kPa, and strain at break s = 305%. The electrode withstands large strains without delamination, shows no conductivity losses during repeated operation for 500 000 cycles, and has an excellent recovery of electrical properties upon being stretched at strains of up to 180%. Reliable prototype capacitive sensors and stack actuators are manufactured by screen-printing the conductive composite on the dielectric film. Stack actuators manufactured from dielectric and conductive materials that are synthesized solvent-free are demonstrated. The stack actuators even self-repair after a breakdown event.