The arsenate(V) NaTi2[AsO4]3 has been synthesized by a solid-state reaction route using a salt flux. Its structure has been solved and refined from single-crystal X-ray data: NASICON-type, R3̄c, a = 8.8057(5), c = 22.2406(15) Å, Z = 6, wR(F2) = 0.0617 for 576 unique reflections and 30 variables. The NaTi2[AsO4]3 structure consists of a three-dimensional framework of corner-sharing AsO4 tetrahedra and TiO6 octahedra. The negatively charged [Ti2As3O12] framework gives rise to two different interstices. The Na+ cation is located on the 6b position with a trigonal antiprismatic coordination and enhanced anisotropic displacement parameters.