Abstract We report on an experimental and theoretical study of strong-field laser ionization of CF₃Br followed by resonant x-ray absorption at the Br K-edge. Distinct 1s → 4p, 5p Rydberg transitions of Br ^q+ (q = 1–4) atomic ions are observed and identified with Hartree–Fock–Slater and relativistic configuration interaction calculations. Time-dependent density functional theory and ab initio molecular dynamics calculations were performed to simulate the dissociative ionization process and the molecular orbitals for the q = 1–4 charge states. Measurements were made with both parallel and perpendicular linear polarizations of the laser and x-rays, but dichroism was not observed, indicating negligible alignment by the laser ionization process. This result is explained by calculations on atomic Br and the molecular simulation.