The new compound La5NbMo2O16 with high ionic conduction has been discovered during the study of the ternary phase diagram of La2O3-MoO3-Nb2O5. The material crystallizes in the cubic space group Pn 3n (no 222) with the unit cell parameter a=11.2250(1) Å. La5NbMo2O16 is a new analogue of the R5Mo3O16 series (R=Pr, Nd). The structure was refined from a combined data X-ray and neutron powder diffraction. The ionic conductivity of the compound is then measured on sintered pellets, by means of complex impedance spectroscopy. © 2016 Elsevier Inc. All rights reserved.