Polystyrene (PS) hollow spheres containing a hole on the surface were used as templates to fabricate double-shelled polypyrrole (PPy) hollow particles with a unique structure similar to that of a thermal bottle. Thanks to the hole on the surface, the monomer and initiator could easily and quickly diffuse into the interior of the PS hollow sphere to generate uniform PPy coatings on both the inner and outer surfaces of the hollow template. When the PS template was selectively removed with tetrahydrofuran, we obtained a double-shelled hollow particle with a structure resembling that of a thermal bottle. We also demonstrated that the morphology and porosity of the resultant PPy coatings could be manipulated and fine-tuned by adjusting at least three parameters: the concentration of monomer, the polymerization time, and the addition of poly(vinyl pyrrolidone).