In this work, we report the preparation of polypyrrole nanowires with ordered large mesopores (OMPW) by a simple chemical polymerization method from dual templates synthesized by self-assembling silica nanospheres in porous anodic aluminum oxide (AAO) membrane channels. The obtained OMPW showed a large surface area (231.5 m2 g−1), high aspect ratio, and interconnected large mesopores (~23 nm). The OMPW was tested as a supercapacitor electrode and showed a specific capacitance of 453 F g−1 at 0.25 A g−1. A sulfur/OMPW (S/OMPW) cathode was fabricated via a simple solution method and a heat-treatment process for lithium/sulfur batteries (LSBs). The S/OMPW composite delivered a large discharge capacity reaching 1601 mAh g−1 at the initial cycle, retaining 1014 mAh g−1 at the 100th cycle at 0.1 C. The great electrochemical performances of the OMPW capacitor electrode and S/OMPW composite were attributed to the large specific surface areas and interconnected mesopores that could supply more active sites for the electrochemical reaction and facilitate mass transfer.