Five new mixed-valence NpV/AnVI molybdates of the composition [C(NH2)3]3[(NpVO2)(NpVIO2)(MoO4)3(H2O)]·H2O (1), [C(NH2)3]3[(NpVO2)(NpVIO2)(MoO4)3(H2O)]·3H2O (2), Na3[(NpVO2)(PuVIO2)(MoO4)3(H2O)]·nH2O (3), Na6[(NpVO2)2(UVIO2)(MoO4)5]·13H2O (4), and LiNa2[(NpVO2)(NpVIO2)2(MoO4)4(H2O)]·4H2O (5) have been synthesized and structurally characterized. The coordination polyhedra of the NpV and AnVI atoms in compounds 1-5 are pentagonal bipyramids. The basis of structures 1-3 is anionic layers of the composition [(NpVO2)(AnVIO2)(MoO4)3(H2O)]n3n-. Three crystallographically independent molybdate ions are tridentate-bridging ligands. The water molecule, which is a part of the anion layer, is coordinated to the NpV atom. The anionic layers in complexes 2 and 3 have the same structure, different from 1. The basis of structure 4 is anionic layers of the composition [(NpVO2)2(UVIO2)(MoO4)5]n6n-, the structure of which differs from the structure of anionic layers in 1-3. Complex 5 has a three-dimensional (3D) structure. The spectra of all compounds in the UV-visible and IR ranges were measured and analyzed.