<p>The unique chemical properties of actinyl hold significant practical importance in the domain of radioactive waste treatment. The advancement of highly efficient ligands for the targeted extraction and stabilization of actinyl ions has become a key research focus, and salophen has demonstrated excellent chelating ability toward actinide ions. In this work, actinyl (VI, V) (An = U, Np and Pu) complexes of the triplesalophen have been systematically investigated. Triplesalophen, possessing multiple N2–O2 binding sites, demonstrates exceptional coordination ability with actinides. The structural geometry, bond characteristics, and thermodynamic properties of the actinyl (VI, V) complexes have been comprehensively investigated via scalar relativistic DFT calculations. Actinyl (V, VI) complexes exhibit shorter An-O bond lengths compared to An-N bonds as well as the larger An-O bond WBIs, which confirms that oxygen is the predominant donor atom to binding actinyl ions. Natural population analysis has revealed that actinyl (VI) complexes display more substantial ligand-to-actinyl charge transfer than their actinyl (V) analogues. Thermodynamic analysis indicated that the complexation of actinides (VI and V) with triplesalophen in aqueous phase is spontaneous. Specifically, Pu (VI) and Np (V) exhibit the highest selectivity among actinide cations at their respective oxidation states. Furthermore, IR spectra were analyzed to identify the interaction modes between actinyl ions and triplesalophen. This work is anticipated to deliver valuable insights and theoretical guidance for the future design of multi-salophen complexes for actinide recognition and extraction.</p> Graphical abstract <p></p>