A synthesis of Li3V2(PO4)3 being a potential cathode material for lithium ion batteries was attempted via a glass-ceramic processing. A glass with the composition of 37.5Li2O–25V2O5–37.5P2O5 (mol%) was prepared by a melt-quenching method and precursor glass powders were crystallized with/without 10wt% glucose in N2 or 7%H2/Ar atmosphere. It was found that heat treatments with glucose at 700°C in 7%H2/Ar can produce well-crystallized Li3V2(PO4)3 in the short time of 30min. The battery performance measurements revealed that the precursor glass shows the discharge capacity of 14mAhg−1 at the rate of 1μAcm−2 and the glass-ceramics with Li3V2(PO4)3 prepared with glucose at 700°C in 7%H2/Ar show the capacities of 117–126mAhg−1 (∼96% of the theoretical capacity) which are independent of heat treatment time. The present study proposes that the glass-ceramic processing is a fast synthesizing route for Li3V2(PO4)3 crystals.