A Prussian blue (PB) type material containing hexacyanovanadate(III), Mn-II (1.5)[V-III(CN)(6)] .0.30MeCN (1), was formed from the reaction of [VIII(CN)(6)](3-) with [Mn(NCMe)(6)](2+) in MeCN. This new material exhibits ferrimagnetic spin- or cluster-glass behavior below a T, of 12 K with observed magnetic hysteresis at 2 K (H-cr = 65 Oe and Kern = 730 emu.Oe/mol). Reactions of [V-III(CN)(6)](3-) with [M-II(NCMe)(6)](2+) (M = Fe, Co, Ni) in MeCN lead to either partial (M = Co) or complete (M = Fe, Ni) linkage isomerization, resulting in compounds of (Fe0.5VIII)-V-II[Fe-II(CN)(6)].0.85MeCN (2), (NEt4)0.10Co(1.5-a)(II)V(a)(II)[Co-III(CN)(6)](a)[V-III(CN)(6)](1-a)(BF4 )(0.10).0.35MeCN (3), and (NEt4)(0.20)V-III(Ni-II(CN)(4)](1.6).0.10MeCN (4) compositions. Compounds 2-4 do not magnetically order as a consequence of diamagnetic cyanometalate anions being present, i.e., [Fe-II(CN)(6)](4-), [Co-III(CN)(6)](3-), and [Ni-II(CN)(4)](2-). Incorporation of [V-III(CN)(6)](3-) into PB-type materials is synthetically challenging because of the lability of the cyanovanadate(III) anion.