Absolute single photoionization cross-section measurements of Rb2+ ions were performed using synchrotron radiation and the photo-ion, merged-beams technique at the Advanced Light Source at Lawrence Berkeley National Laboratory. Measurements were made at a photon energy resolution of 13.5 2.5 meV from 37.31 to 44.08 eV spanning the 2P ground state and 2P metastable state ionization thresholds. Multiple autoionizing resonance series arising from each initial state are identified using quantum defect theory. The measurements are compared to Breit-Pauli R-matrix calculations with excellent agreement between theory and experiment.