The steric and electronic factors that influence which of the two rings of a substituted biphenyl ligand coordinates to chromium are of interest and it has been suggested that haptotropic rearrangements within these molecules may be limited if the arene-arene dihedral angle is too large. Two tricarbonylchromium(0) complexes and their respective free ligands have been characterized by single-crystal X-ray diffraction. In the solid state, tricarbonyl[(1′,2′,3′,4′,5′,6′-η)-2-fluoro-1,1′-biphenyl]chromium(0), [Cr(C12H9F)(CO)3], (I), exists as the more stable isomer with the nonhalogenated arene ring ligated to the metal center. Similarly, tricarbonyl[(1′,2′,3′,4′,5′,6′-η)-4-fluoro-1,1′-biphenyl]chromium(0) crystallizes as the more stable isomer with the phenyl ring bonded to the Cr0 center. The arene-arene dihedral angles in these complexes are 55.77 (4) and 52.4 (5)°, respectively. Structural features of these complexes are compared to those of the DFT-optimized geometries of ten tricarbonyl[(η6-C6H5)(4-F-C6H4)]chromium model complexes. The solid-state structures of the free ligands 2-fluoro-1,1′-biphenyl and 4-fluoro-1,1′-biphenyl, both C12H9F, exhibit arene-arene dihedral angles of 54.83 (7) and 0.71 (8)°, respectively. The molecules of the free ligands occupy crystallographic twofold axes and exhibit positional disorder. Weak intermolecular C-H⋯F interactions are observed in all four structures. © 2017 International Union of Crystallography.