In this paper, the electrochemical impedance analysis of MgHf4P6O24 electroceramic oxide electrolyte on platinised pellets of 13mm diameter (Ø) and 3.8mm thickness depicts the electrical properties of Mg 2+ -cation conducting species in the characterised solid-state electrolytes measured using the two-probe analysis at 182-764 o C, and from 100mHz to 32MHz, were evaluated. In this analysis, promising ionic conductivity of 4.52 x 10 -4 Scm -1 for MgHf4P6O24 electroceramic electrolyte was exhibited at 747 o C, thereby maintaining both materials and operational stability at 1000 o C ≤ T/ o C≤1300.In addition to this, the design, fabrication and testing of solid-state Mg-sensors using the electrochemical method have been achieved. The novel high-temperature Mg-sensors were designed using the highly conducting Mg 2+ -cation solid-state electrolyte by incorporating a biphasic powder mixture of MgCr2O4 + Cr2O3 as ceramic solid-state reference electrode in air, which has shown promising trend after successfully sensing the Mg dissolved in molten Al at 700±5 o C. A linear dependence of emf on logarithm of Mg concentration was achieved. The transport number, tmg2+ = 0.84±0.03 was achieved which indicates that the conducting specie in MgHf4P6O24 solid-state electrolyte is Mg 2+ -cation. The solid-state electrolyte has the potential for application in high-temperature electrochemical sensors and other devices.