We have performed Monte Carlo simulations of lithium at high temperatures in the isothermal-isobaric and canonical ensembles, using plane-wave density functional theory to provide configurational energies. This is made computationally feasible by the use of an 'approximate' empirical potential to generate large Monte Carlo moves with a high likelihood of acceptance. We discuss both simulation results and implementation details. Reasonable results are obtained at high temperatures, though all levels of theory considered systematically overestimate the liquid density. (c) 2005 Elsevier B.V. All rights reserved.