Investigations on the glass system mol% 50Li(2)O:(50-x)P2O5:xB(2)O(3) reveal that the glass forming region is limited to a small region of 0 <= x <= 20. Addition of B2O3 is found to enhance the thermal stability of the glasses. Raman spectra reveal that the glass matrix undergoes structural modification for x >= 15, with the formation of borophosphate structural units, due to the presence of which, the glass composition 50Li(2)O: 30P(2)O(5): 20B(2)O(3) has exhibited dc conductivity value of 1.8 x 10(-5) S cm(-1), when compared to the value of 8.4 x 10(-7) S cm(-1) of 50Li(2)O: 50P(2)O(5) at 110 degrees C. Though ball milled sample for x = 15 initially exhibited better conduction characteristics than melt quenched ones, the conductivity decreased during thermal cycling process probably due to the phase instability of the milled samples. The frequency dependent conductivity plots have been scaled to a single master curve indicating temperature independent relaxation mechanism. (c) 2008 Elsevier B.V All rights reserved.