Solid electrolytes are highly important materials for improving safety, energy density, and reversibility of electrochemical energy storage batteries. However, it is a challenge to modulate the coordination structure of conducting ions, which limits the improvement of ionic conductivity and hampers further development of practical solid electrolytes. Here, we present a skeleton-retained cationic exchange approach to produce a high-performance solid electrolyte of Li
3
Zr
2
Si
2
PO
12
stemming from the NASICON-type superionic conductor of Na
3
Zr
2
Si
2
PO
12
. The introduced lithium ions stabilized in under-coordination structures are facilitated to pass through relatively large conduction bottlenecks inherited from the Na
3
Zr
2
Si
2
PO
12
precursor. The synthesized Li
3
Zr
2
Si
2
PO
12
achieves a low activation energy of 0.21 eV and a high ionic conductivity of 3.59 mS cm
−1
at room temperature. Li
3
Zr
2
Si
2
PO
12
not only inherits the satisfactory air survivability from Na
3
Zr
2
Si
2
PO
12
but also exhibits excellent cyclic stability and rate capability when applied to solid-state batteries. The present study opens an innovative avenue to regulate cationic occupancy and make new materials.
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