A new type of polyoxomolybdate containing mixed-valence arsenic, [AgAs(III)(2)(As(III)As(V)Mo(4)O(18)(OH)(2))(3)](11-) (1), has been synthesized. Single-crystal X-ray analysis was carried out on (NH(4))(5)(C(2)H(9)N(2))(4.5)H(1.5)[AgAs(III)(2)(As(III)As(V)Mo(4)O(18)(OH)(2))(3)]·14H(2)O (1a) and (NH(4))(11)[AgAs(III)(2)(As(III)As(V)Mo(4)O(18)(OH)(2))(3)]·16H(2)O (1b). The polyanion is composed of three unprecedented [As(III)As(V)Mo(4)O(18)(OH)(2)](6-) subunits linked together by two AsO(3) trigonal-pyramidal structures from both sides via sharing six bridging oxygen atoms, and a silver cation is enclosed in the center of the polyanion and coordinated by three As atoms with the As-Ag-As bond angle of 120°, to lead to a fan-like structure with an approximative C(3h) symmetry. The polyanion was also characterized by IR, X-ray photoelectron spectroscopy and thermogravimetry-differential scanning calorimetry. The stability of [AgAs(III)(2)(As(III)As(V)Mo(4)O(18)(OH)(2))(3)](11-) in an aqueous solution was investigated by electronic absorbance spectroscopy and electrospray ionization mass spectrometry, and the possible disaggregation mechanism of the polyanion is proposed.