Based on these experiments, the following mechanisms for the formation of the particles and the gelation are proposed (Fig. ). During the oxidative polymerization of EDOT in the presence of PSS-b-PNIPAM (below the LCST), PEDOT + chains grow and complex with the PSS -block. This polyelectrolyte complex is likely more hydrophobic than PNIPAM which results in the formation of spherical/ovoid particles with a PEDOT:PSS core and PNIPAM shell. The presence of PNIPAM in the shell is consistent with results from the surface elemental analysis by X-ray photoelectron spectroscopy (XPS), showing that the ratio of N:S is always higher (6.34 ± 0.36) than the theoretical N:S ratio of 4.5:1 (Fig. ). In some cases, these disk-spheres are assembled in wormlike chains, likely through the polymerization of longer PEDOT chains within the core of the colloidal particles that forced the fusion of the spherical/ovoid particles. Occurrences of lamellar fringes outside the disk-spheres were seen on the cryo-EM, implying that some PEDOT also polymerized outside the shell and was electrostatically bound to the colloidal particles. Postsynthesis and above the LCST at a concentration of 3.6 wt%, the colloidal particles aggregate into a bi-continuous network while generally maintaining (or perhaps slightly increasing) their overall size, which leads to gelation. This aggregation can be attributed to inter-molecular hydrogen bonding of the PNIPAM domains above the LCST while the PEDOT:PSS core remained unchanged, consistent with results from Raman spectroscopy (SI Section 3.7, Fig. , Table ).