© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Carbonaceous materials have emerged as promising anode candidates for potassium-ion batteries (PIBs) due to overwhelming advantages including cost-effectiveness and wide availability of materials. However, further development in this realm is handicapped by the deficiency in their in-target and large-scale synthesis, as well as their low specific capacity and huge volume expansion. Herein the precise and scalable synthesis of N/S dual-doped graphitic hollow architectures (NSG) via direct plasma enhanced chemical vapor deposition is reported. Thus-fabricated NSG affording uniform nitrogen/sulfur co-doping, possesses ample potassiophilic surface moieties, effective electron/ion-transport pathways, and high structural stability, which bestow it with high rate capability (≈100 mAh g−1 at 20 A g−1) and a prolonged cycle life (a capacity retention rate of 90.2% at 5 A g−1 after 5000 cycles), important steps toward high-performance K-ion storage. The enhanced kinetics of the NSG anode are systematically probed by theoretical simulations combined with operando Raman spectroscopy, ex situ X-ray photoelectron spectroscopy, and galvanostatic intermittent titration technique measurements. In further contexts, printed NSG electrodes with tunable mass loading (1.84, 3.64, and 5.65 mg cm−2) are realized to showcase high areal capacities. This study demonstrates the construction of a printable carbon-based PIB anode, that holds great promise for next-generation grid-scale PIB applications.