7Li magnetic resonance spectroscopy (MRS) has been successfully used in recent years as a new tool to measure brain tissue lithium concentrations in vivo. After demonstration of its feasibility in animal studies over a decade ago, human investigations have characterized the brain pharmacokinetics of lithium. Preliminary studies have investigated brain pharmacokinetic correlates of clinical response in the treatment of bipolar disorder patients, with indication of possible clinical relevance of 7Li MRS measures. In this paper we reviewed the accumulated literature in this area, and discuss possible directions for this research in the context of preliminary studies conducted by our group that demonstrated the feasibility of 7Li MRS at 3 T.