The shuttle effect and excessive volume change of the sulfur cathode severely impede the industrial implementation of Li-S batteries. It is still highly challenging to find an efficient way to suppress the shuttle effect and volume expansion. Here, we report, for the first time, an innovative atomic orbital hybridization concept to construct the hierarchical hollow sandwiched sulfur nanospheres with double-polyaniline layers as the cathode material for large-scale high-performance Li-S batteries. This hierarchically 3D, cross-linked and stable sulfur-polyaniline backbone with interconnected disulfide bonds provides a new type and strong intrinsic chemical confinement of sulfur owing to the atomic orbital hybridization of Li 2s, S 3p, C 2p and N 2p. Crucially, such atomic orbital hybridization of sulfur sandwiched in the double sulfur-polyaniline network is highly reversible during the discharge/charge process and can very efficiently suppress the shuttle effect and volume expansion, contributing to a very high capacity of 1142 mAh g-1 and an excellent stabilized capacity of 886 mAh g-1 at 0.2 C after 500 cycles with a suppressed volume expansion and an unprecedented electrode integrity. This innovative atomic orbital hybridization concept can be extended to the preparation of other electrode materials to eliminate the shuttle effect and volume expansion in battery technologies. The present work also provides a commercially viable and up-scalable cathode material based on this strong and highly reversible atomic orbital hybridation for large-scale high-performance Li-S batteries.