Recent increasing demand for new eco-friendly materials and for low cost fabrication process for use in optical sensors field, raise concern about alternative materials for this application. We have designed two glass-ceramics compositions from the quaternary ROAl2O3- SiO2-B2O3(R=Ba) alkali-earth aluminum silicate system, labeled B72 and B69, with high refractive index (>1.6), large values of Abbe number (94.0 and 53.0, respectively), and free of lead and arsenic. We present an analysis and discussion of experimental optical properties, thermal and thermo-chemical stability along with important properties such as transition temperature (Tg), onset of crystallization (Tx) as well transport properties as ionic conductivity behavior in the quaternary glass-ceramic system containing boron for use as optical sensors. Complex Impedance Spectra (Bode Plot) and Potentiodynamic Polarization curves (Tafel plots) measurements were carried out in the temperature range of 600 to 850°C. The most probable conductivity mechanism is a thermally activated process of mobile ions overcoming a potential barrier (EA), according to the Arrhenius regime. Here we report that charge transfer is caused by the flux of electrons, in the region of elevated temperatures (>700°C), and is affected by immiscibility of crystals, nucleation and growth type, that causes phase separation. We found conductivity (σ) values from 10-9 to 10-5 S/cm at temperatures between 700 and 850°C. Our results highlight a need for research on ion mobility in the glassy network above the transition range, and the effect cause by metastable immiscibility in the alkaline-earth glasses are exposed. The two glass compositions B72 and B69 can be tailored by proper use as glassy optical sensor.