The tite compound, lithium penta-sodium nona-molybdate, LiNa(5)Mo(9)O(30), was synthesized by solid-state reaction. The three-dimensional [Mo(9)O(30)](6-) framework is built up from MoO(6) octa-hedra and MoO(5) bipyramids, linked together by edges and corners. The framework delimits two types of inter-secting tunnels running along [100] and [010] in which the Na(+) and Li(+) ions are located. The asymmetric unit contains one Mo, one Na and one Li site located on a twofold rotation axis. The crystal studied was a racemic twin with site a twin ratio of 0.51 (10):0.49 (10). Relationships between the structures of K(2)Mo(3)O(10), K(2)Mo(4)O(13), Cs(2)Mo(7)O(22), Na(6)Mo(10)O(33) and Na(6)Mo(11)O(36) compounds are discussed.