An initial survey of the 95Mo n.m.r. properties of a range of 12 polyoxomolybdates is presented. The species resonate in the range - 18 to + 140 ppm. The observed line widths generally exceed 100 Hz for six-coordinate molybdenum sites of low symmetry, but can be narrow (< 20 Hz at 20�) for four-coordinate sites. Aqueous solutions of [Mo7O24]6- at pH 6.1 exhibit exchange between Mo- and Mo7-based species. Solutions of α-[Mo8O26]4- in MeCN feature a single narrow resonance (δ16, Wh/2 23 Hz at 20�) assigned to the tetrahedral capping sites, while two broad resonances (δ19, Wh/2 240 Hz; δ109, Wh/2 C. 270 HZ) are seen in equivalent solutions of β-[Mo8O26]4-. In the cases cited above, 17O n.m.r. is used to confirm the integrity of sample solutions and assists in correction of the 95Mo n.m.r. properties of β-[Mo8O26]4 reported in a previous communication.