AbstractThe glass-ceramics of the phosphorus containing Na5RSi4O12type (R=rare earth) Na+-superionic conductors (Narpsio-V) in the system Na2O-Sm2O3-P2O5-SiO2 were prepared by crystallization of glasses with the composition Na3+3x-ySm1-xPySi3-yO9. The optimum conditions for crystallization were discussed with reference to the conduction properties and the preparation of uncracked bulky glass-ceramic Narpsio-V. The ionic conductivity of the glass-ceramic Na3.9Sm0.6P0.3Si2.7O9 at 300°C was drastically enhanced from 2.38×10-2 S/cm to 7.15×10-2 S/cm upon implantation of 200 keV Na+ ions to a fluence of 1 × 1015 cm-2.