Actinide chemistry is gaining increased focus in modern research, particularly in the fields of energy research and molecular magnetism. However, the structure-function and structure-property relationships of actinides have still not been studied as intensely as those for transition metals. In this work, we report a detailed ab initio study of the spectroscopic, magnetic, and bonding properties of the trivalent actinide free ions and their associated hexachloride complexes in octahedral symmetry. The electronic structures of these systems are examined using complete active-space self-consistent-field calculations followed by second-order N-electron valence perturbation theory, including both scalar relativistic and spin-orbit-coupling effects. The computed energies and wave functions are further analyzed by means of ab initio ligand-field theory (AILFT) and finally chemically interpreted by means of the angular overlap model (AOM). The derived Slater-Condon and spin-orbit parameters have allowed us to systematically rationalize the spectroscopic and magnetic properties of the investigated free ions and complexes along the entire actinide series. Overall, the AILFT- and AOM-derived parameters accurately reproduce the multireference electronic structure calculations. The small observed discrepancies with respect to experimentally derived ligand-field parameters are essentially due to an underestimation of the electronic correlation, which arises from both the constrained size of the active space (restricted to the f orbitals) and the limit of the perturbation approach to account for dynamical correlation. Our analysis also provides insight into the metal-ligand covalency trends along the series. Consistent with natural population analysis, the nephelauxetic (Slater-Condon parameters) and relativistic nephelauxetic (spin-orbit-coupling) reductions determined for these complexes indicate a decrease in the covalency along the series. These trends also hold, to varying extents, for the corresponding tetravalent derivatives, as well as the lanthanide analogues.