The benzene-lithium complex is a prototype system to understand the interaction in lithium-doped nanocarbons. Herein, we have employed coupled-cluster theory and correlation consistent basis sets to study the C-6v and C-2v structures, of the C6H6 center dot Li complex. We found that when the CCSD(T) method and large basis sets are employed, the C-2V structure becomes lower in energy by 1.8 kcal/mol. At the CCSD(T)/CBS level, and including corrections for core-valence and relativistic effects, the dissociation energy of the C-2v (ionic) structure is 6.7 kcal/mol whereas that corresponding to the C-6v (nonionic) one is 4.9 kcal/mol. Our results suggest that charge transfer in C6H6 center dot Li does exist, in contrast with previous results. (C) 2013 Elsevier B. V. All rights reserved.