Trilithium aluminium trimolybdate(VI), Li(3)Al(MoO(4))(3), has been grown as single crystals from α-Al(2)O(3) and MoO(3) in an Li(2)MoO(4) flux at 998 K. This compound is an example of the well known lyonsite structure type, the general formula of which can be written as A(16)B(12)O(48). Because this structure can accomodate cationic mixing as well as cationic vacancies, a wide range of chemical compositions can adopt this structure type. This has led to instances in the literature where membership in the lyonsite family has been overlooked when assigning the structure type to novel compounds. In the title compound, there are two octahedral sites with substitutional disorder between Li(+) and Al(3+), as well as a trigonal prismatic site fully occupied by Li(+). The (Li,Al)O(6) octahedra and LiO(6) trigonal prisms are linked to form hexagonal tunnels along the [100] axis. These polyhedra are connected by isolated MoO(4) tetrahedra. Infinite chains of face-sharing (Li,Al)O(6) octahedra extend through the centers of the tunnels. A mixed Li/Al site, an Li, an Mo, and two O atoms are located on mirror planes.