The separation and management of nuclear waste is one of the problems that needs to be solved urgently, so finding a new radiation-proof and durable extractant to deal with nuclear waste is a difficult but desirable task. Since the successful isolation of the first pentavalent plutonium crown ether complex recently (Wang et al. CCS Chem. 2020, 2, 425-431), complexes with actinyl(V/VI) inserted into the cavity of 18-crown-6 ether (oxo-18C6), as well as their bonding character, need to be explored. Here we present a series of novel crown ether complexes containing actinyl(V/VI) and oxo-18C6 via computational prediction and analysis. On the basis of the calculations, actinyl(V/VI) are thermodynamically feasible and can be stabilized by oxo-18C6 ligand via six dative bonds between An ions and the oxo-18C6 O atoms in the "insertion" structure of [AnO(2)(18C6)](2+/+) complexes. The stability of actinyl(VI) species generally falls at minor actinides, ascribed to the reduced highest possible oxidation states of curium, which is mainly attributed to the mixing of bonding orbitals and non-bonding orbitals as well as the increase of occupation on partially 5f antibonding orbitals. It is found that the interactions between the actinyl(V/VI) and oxo-18C6 are mainly electronic interactions, with the well-known covalency contributions generally decreasing from uranium to curium due to energy degeneracy and spatial orbital contraction. This work would give a basic understanding of the coordination chemistry of actinyl(V/VI), which also provides inspirations on the design of new extractants for actinide separations.