We report on the observation of blue-detuned photoassociation in Rb(2), in which vibrational levels are energetically above the corresponding excited atomic asymptote. (85)Rb atoms in a MOT were photoassociated at short internuclear distance to levels of the 1(3)Π(g) state at a rate of approximately 5 × 10(4) molecules s(-1). We have observed most of the predicted vibrational levels for all four spin-orbit components; 0(+)(g), 0(-)(g), 1(g), and 2(g), including levels of the 0(+)(g) outer well. These molecules decay to the metastable a(3)Σ(+)(u) state, some preferentially to the v'' = 0 level, as we have observed for photoassociation to the v' = 8 level of the 1(g) component.