Two novel hybrid polyoxovanadates that are functionalized by (4-aminophenyl)arsonic acid ligands form upon the reduction of vanadates(V) in aqueous systems, whereby the underlying condensation reactions are influenced by the nature of the employed acid. In the presence of Cl- ions that derive from hydrochloric acid, a tetradecanuclear cage structure [(V14O16)-O-IV(OH)(8)-(O3AsC6H4-4-NH2)(10)](4-), whose cavity contains stabilizing halide ions and water molecules, is obtained. When nitric acid is used, a decanuclear [V10O8(O3AsC6H4-4-NH2)(7)(DMF)(2)](5-) cluster can be isolated. The latter organizes into a hexagonal packing arrangement in the solid state.