Polypyrrole–polyethylene glycol (PPy/PEG)-modified sulfur/aligned carbon nanotubes (PPy/PEG–S/A-CNTs) were synthesized by using an in situ polymerization method. The ratio of PPy to PEG equaled 31.7:1 after polymerization, and the PEG served as a cation dopant in the polymerization and electrochemical reactions. Elemental analysis, FTIR, Raman spectroscopy, XRD, and electrochemical methods were performed to measure the physicochemical properties of the composite. Elemental analysis demonstrated that the sulfur, PPy, PEG, A-CNT, and chloride content in the synthesized material was 64.6 %, 22.1 %, 0.7 %, 12.1 %, and 0.5 %, respectively. The thickness of the polymer shell was about 15–25 nm, and FTIR confirmed the successful PPy/PEG synthesis. The cathode exhibited a high initial specific capacity of 1355 mAh g−1, and a sulfur usage of 81.1 %. The reversible capacity of 924 mAh g−1 was obtained after 100 cycles, showing a remarkably improved cyclability compared to equivalent systems without PEG doping and without any coatings. PPy/PEG provided an effective electronically conductive network and a stable interface structure for the cathode. Rate performance of the PPy/PEG– S/A-CNT composite was more than double that of the unmodified S/A-CNTs. Remarkably, the battery could work at a very high current density of 8 A g−1 and reached an initial capacity of 542 mAh g−1; it also retained a capacity of 480 mAh g−1 after 100 cycles. The addition of PEG as a dopant in the PPy shell contributed to this prominent rate improvement. Lithium ions and electrons were available everywhere on the surfaces of the particles, and thus could greatly improve the electrochemical reaction; PEG is a well-known solvent for lithium salts and a very good lithium-ion catcher.