The xLi2O.ySiO2.zCaO (1-x-y-z)B2O3 glass system (where x = 0, 5, 10, 15, 20 and 25 mol%, y=60 mol% and z=10 mol%) was processed through a dissolved quench technique. To acquire the structural performance of silica, calcium, boron and oxygen were minutely observed by using Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction. The position and relative quantities of IR bands responsible for the distinct silicate and borate units were determined using deconvoluted spectra. For the increased amount of B2O3 the results show that BO3 occupies the network position and creates the linkage SiO-Ca. The bands related to the bending mode of H2O molecules and the stretching mode of B—O—H groups forming hydrogen bonding are shown to result in several bands: 23002380cm-1 and 2820-3505 cm-1 respectively. The XRD order of the base samples exhibited homogeneous glasses and also an optical reconnoitre, but did not show any phase separation record.