The synthesis and characterization of four Lewis base-free, sigma-bonded lithium aryls are reported. This work was undertaken in order to provide a model for the solid-state structure of phenyllithium, which is currently unknown. Nondonor hydrocarbon solubility of the four lithium aryls (LiC6H3-3,5-t-Bu(2))(6) (1), (LiC6H4-4-t-Bu)(n) (2), (LiC6H4-4-n-Bu)(n) (3), and {LiC6H4-4-SiMe(2)(t-Bu)}(n) (4) was achieved by the incorporation of meta- or para-substituents on the aryl rings. This permitted C-13 NMR spectroscopy and crystal growth using their solutions. It is proposed that the absence of bulky ortho-substituents allows association of the Lithium aryls to occur in a manner similar to that of phenyllithium itself. The C-13 NMR data for the ipso-carbon atoms suggest an association number of at least four or, more probably, six in solution. These data are in agreement with the X-ray crystal structure of 1, which is hexameric, with a distorted octahedral (trigonal antiprismatic) array of lithium ions. Six of the eight Lis faces are capped by an aryl group that interacts primarily through the C(ipso) atom. Weaker Li-C(ortho) interactions are also apparent. This structure is the first of this type for an unsolvated, sigma-bonded Lithium aryl. Crystal data with Cu K alpha (lambda = 1.541 78 Angstrom) radiation for 1 at 130 K : 1, C84H126Li6, M = 1177.49, a = 13.516(2) Angstrom, b = 15.124(3) Angstrom, c = 20.958(3) Angstrom, alpha = 84.084(13)degrees, beta = 86.249(11) Angstrom, gamma = 68.675(13)degrees, V = 3967.7(11) Angstrom(3), Z = 2, space group , R(1) = 0.085 for 7983 (I > 2 sigma(I)) data.