We prove the first correction to the leading Thomas-Fermi energy for the ground state energy of atoms and molecules in a model where the kinetic energy of the electrons is treated relativistically. The leading Thomas-Fermi energy, established in [25], as well as the correction given here, are of semiclassical nature. Our result on atoms and molecules is proved from a general semiclassical estimate for relativistic operators with potentials with Coulomb-like singularities. This semiclassical estimate is obtained using the coherent state calculus introduced in [36]. The paper contains a unified treatment of the relativistic as well as the nonrelativistic case. © 2009 Wiley Periodicals, Inc.