The conductivity of the Li2O:P2O5:MO3 (M = Cr2, Mo, W) glasses increases as P2O5 is progressively substituted by MO3 and as the Li2O content increases. Amongst the glass compositions studied, the 0.50Li2O:0.20P2O5:0.30WO3 glass has the highest conductivity at 25°C of 2. 1×10−6 ×−1 cm−1. The glass transition temperature of the glasses increases initially with network former substitution, reaches a maximum at around MO3/P2O5 = 1, and decreases with further substitution. X-ray photoelectron spectroscopy reveals the presence of M ions in more than one oxidation state and oxygen species such as P=O, P-O-P, P-O, M-O-M, M-O and P-O-M. Raman spectroscopy shows that the Li2O:P2O5:MoO3 and Li2O:P2O5:WO3 glasses consist of PO4, MoO4 (WO4) and MoO6 (WO6) polyhedra while the Li2O:P2O5:Cr2O3 glasses consist of the PO4 and CrO6 polyhedra only. The phosphate groups are preferentially modified by Li2O in comparison with the tungstate, molybdate and chromate groups. The increasing number of non-bridging oxygen atoms per phosphate group may be related to the increasing conductivity with the progressive substitution of MO3 for P2O5.