Transparent glasses embedded with ferroelectric/nonlinear optic crystallites have been in increasing demand as these exhibit promising physical properties. These could be fabricated in large sizes and shapes with high optical homogeneity accompanied by high degree of transparency over a wide range of wavelengths of light. Amongst a variety of glasses that are known, borate-based glasses are of particular interest owing to their greater transparency, good chemical and mechanical stability, low materials cost, and useful electrical and dielectric properties. Keeping the potential multifarious applications of transparent glass-microcrystal composites in view, BaO-0.5Na2O-4.5B2O3, BaO-0.5Li2O-4.5B2O3, SrO-0.5Li2O-4.5B2O3, 3BaO-3TiO2-B2O3 and Li2O-3B2O3 glasses and glass-microcrystal composites were fabricated. These glasses on controlled heat treatment at appropriate temperatures yielded BaNaB9O15, BaLiB9O15, SrLiB9O15, Ba3Ti3B2O12 and LiB3O5 crystalline phases, respectively. Further transparent surface crystallized BaO-0.5Na2O-4.5B2O3 glasses were fabricated using ultrasonic treatment and their thermal properties have been investigated in detail using differential scanning calorimetry. It is observed that these glasses were homogeneously crystallizing on the surfaces after Ultrasonic treatment which can be exploited for planner wave-guide applications. Glass forming ability, thermal stability, glass-transition behavior, crystallization kinetics and viscosity of these glasses were studied extensively using various methods and rationalized by invoking various models. The above glasses have been characterized for their dielectric and electrical relaxation properties (as these properties are related to their electro-optic and non-linear optical properties) over 30- 600oC temperature range and frequencies (100 Hz -10 MHz) that are normally of interest in the applications of these materials. Several interesting features such as high ionic conductivity, marginally low dielectric loss and high dielectric constant behavior along with low thermal coefficient of dielectric constant were observed in these glasses and were rationalized using various models. The combination of these dielectric characteristics suggests that these are potential candidates for electrical energy storage device applications.