Abstract: | Abstract A new synthetic approach for the fabrication of core‐shell like conducting elastomers was described. The approach utilized the facile intermolecular self‐assembly of poly(dimethylsiloxane) (PDMS) in DMSO leading to formation of a core particle, while soluble oligoaniline (A x ) segments dispersed in the solution phase resembling a shell overlayer for building the morphology. This morphology was demonstrated by bis[penta(tetraanilinofullereno)] bis(aminopropyl)poly(dimethylsiloxane) [PDMS‐(F5A4)2] triblock co‐oligomers synthesized using a functionalized C60 derivative as a linker. Observation of 1H NMR spectroscopic responses on the PDMS particle formation in DMSO‐d 6 is consistent with the proposed core‐shell geometry with oligoaniline moieties located at the shell overlayer. |