The preparation and properties of the first strontium-manganese molecular complex are described. The reaction of (NBu4n)[Mn4O2(O2CPh)(9)(H2O)] (4Mn(III)) with Sr(ClO4)(2) in MeCN/MeOH led to the isolation of [SrMn14O11(OMe)(3)(O2CPh)(18)(MeCN)(2)] (1; 13Mn(III), Mn-II). The structure of 1 consists of two [Mn4O3(OMe)] cubane units attached to a central, near-planar, trinuclear [Mn3O4] unit, to which are also attached a Mn and a Sr above the plane and a [Mn2O(OMe)] rhomb below the plane. Peripheral ligation is provided by 18 bridging benzoate and two terminal MeCN groups. Variable-temperature and -field dc magnetization (M) data were collected in the 1.8-10 K and 0.1-4.0 T ranges and fit by matrix diagonalization methods to give S = 9/2, D = -0.50(5) cm(-1), and g = 1.88(10), where S is the ground-state spin and D is the axial zero-field splitting parameter. Magnetization versus dc field sweeps at various temperatures and scan rates exhibited hysteresis loops, confirming 1 to be a new single-molecule magnet. Because complex 1 is the initial molecular example of intimately associated Mn and Sr atoms, Sr EXAFS studies have been performed for the first time on a synthetic Sr-containing molecule. This has also allowed comparisons with the EXAFS data on the Sr-substituted water oxidizing complex (WOC) of Photosystern II (PS II), which contains a SrMn4 complex.