Based on orbital-free ab initio molecular dynamics calculations, the geometries and energetics of lithium-doped aluminium clusters (Al n Li, n = 1, 13) have been investigated. It is seen that, a single impurity of Li affects the geometries of small ( n < 6) clusters, and this effect is less pronounced for larger clusters. The results suggest extra stability for the Al 3Li, Al 6Li and Al 13Li clusters, which are in contrast with our earlier results on Li n Al. The results indicate that the Li atom segregates to the surface of the aluminium cluster and prefers to form a tetrahedron, wherever possible, with one of the triangular faces of Al atoms. In particular, for Al 13Li, the Al 13 core takes the most symmetric icosahedral form with the Li atom occupying the outer ‘hollow-site’.