Redox-active materials with excellent rate capability and cycling performance are in highly demand for electrochemical energy storage and conversion applications. Here, we unveil the confined proton-conduction behavior of one-dimensional polyoxometalate chains inside single-walled carbon nanotubes (SWNTs). The polyoxometalate molecules including phosphomolybdic acid {HPMo} and phosphotungstic acid {HPW} are encapsulated within SWNTs via host–guest recognition, driven by the electron transfer from nanotubes to polyoxometalates. Impressively, the redox hybrids of polyoxometalate@SWNTs deliver abnormal rate performance in acidic solution with capacity retentions over 73 % at high sweep rate of 1000 mV s−1, relative to the capacity at 10 mV s−1. This value is comparable to that of the pure SWNTs, typically known as double-layer capacitive materials. Electrochemical analyses reveal the Grotthuss proton-conduction mechanism of {HPMo} in SWNTs with a low activation energy of 0.11 eV. Therefore, the {HPMo}@SWNT hybrid demonstrates quasi diffusion-free characteristic with dominant capacitive contribution over 60 % at different sweep rates. Molecular dynamic simulations and density functional theory calculations evidence the strong burst-like transport of protons in the {HPMo}@SWNT hybrid. This process is dynamically favored in the continuous and long-range hydrogen-bond network along polyoxometalate chains with bound/free water molecules inside SWNTs. The superiority of nanoconfined Grotthuss mechanism may engender an exciting avenue for developing high-performance energy storage materials.