Amphiphilic copolymers poly(N-(2-methacryloylxy) ethyl pyrrolidone)-block-poly(2-(perfluorooctyl) ethyl methacrylate) (PNMPm-b-PFMAn) with similar m/n of about 10 preferred to form spherical micelles in water regardless of the molecular weight. These PNMPm-b-PFMAn micelles as Pickering emulsifiers commonly favored the formation of O/W Pickering emulsions in the cyclohexane/water systems, and the corresponding interfacial structures were characterized by the confocal laser scanning microscopy (CLSM) method. Moreover, high internal phase Pickering emulsions (HIPPEs) were formed at high volume ratio of oil/water (VO/VW), which were excellent templates in generating structurally well-defined 3D porous PEDOT:PSS aerogels with low density and high conductivity. It was noticed that the HIPPE-templated PEDOT:PSS aerogels were mainly composed of hierarchically connected nano-/micro-level fibers, which were significantly different from the randomly intertangled lamellar micro-belts of PEDOT:PSS aerogels prepared by the hydrogel method under the same conditions. In addition, the HIPPE-templated stretchable and compressible PEDOT:PSS aerogels showed wide strain-invariant resistance (SIR) range and remarkable cycling stability, which were far superior to the hydrogel ones.