AbstractPractical applications of sulfurized polymer (SP) materials in Li–S batteries (LSBs) are often written off due to their low S content (≈35 wt%). Unlike conventional S8/C composite cathodes, SP materials are shown to function as pseudocapacitors with an active carbon backbone using a comprehensive array of tools including in situ Raman and electrochemical impedance spectroscopy. Critical metric analysis of LSBs containing SP materials with an active carbon skeleton shows that SP cathodes with 35 wt% S are suitable for 350 Wh kg−1target at the cell level if S loading >5 mg cm−2, electrolyte‐to‐sulfur ratio <2 µL mg−1, and negative‐to‐positive ratio <5 can be achieved. Although 3D current collectors can enable such high loadings, they often add excess mass decreasing the total capacity. An “active” carbon nanotube bucky sandwich current collector developed here offsets its excess weight by contributing to the electric double layer capacity. SP cathodes (35 wt% S) with ≈5.5 mg cm−2of S loading (≈15.8 mg cm−2of SP loading) yield a sulfur‐level gravimetric capacity ≈1360 mAh gs−1(≈690 mAh gs−1), electrode level capacity 200 mAh gelectrode−1(100 mAh gelectrode−1), and areal capacity ≈7.8 mAh cm−2(≈4.0 mAh cm−2) at 0.1C (1C) rate for ≈100 cycles at E/S ratio = 7 µL mg−1.