A new polyoxometalate compound consisting of the 39-tungsto-4-arsenate(III) unit with four incorporated VIV ions, isolated as (NH4)22[(VIVO)2(VIVO(H2O))(AsIIIWVI9O33)2(AsIIIWVI8.5VIV0.5(OH)O32)2(WVIO2)4]·48H2O (NH4-As4W39(V4)), was synthesized and fully characterized. SQUID magnetometry shows three weakly coupled VIV centers with an antiferromagnetic exchange interaction and one isolated VIV ion as a spin-1/2 Curie paramagnet. UV-vis spectroscopy indicates that the As4W39(V4) structure remains intact in aqueous solution for at least 24 h. To enable the deposition of As4W39(V4) from solution on gold surfaces, its trihexyltetradecylphosphonium salt, THTDP-As4W39(V4), was prepared. The IR spectra of both congeners reveal the structural identity of As4W39(V4) independent of the countercations. The X-ray absorption near-edge structure data confirm the presence of VIV centers in a distorted square-pyramidal coordination geometry in NH4-As4W39(V4) and THTDP-As4W39(V4). X-ray photoelectron spectroscopy of the latter, deposited on Au(111), shows that the 4 V and 35 W centers preserve their IV+ and VI+ oxidation states, while the remaining 4 W ions are reduced to IV+.