Rb vapor was irradiated in a glass fluorescence cell with pulses of radiation from a YAG laser-pumped OPO laser, populating 5Dj (or 7S ) state by two-photon absorption. Energy transfer in Rb (5Dj,7S)+Rb(5S) collision is studied using methods of atomic fluorescence. The resulting fluorescence includes a direct component emitted in the optically excited state decay and a sensitized component arsing from the collisional populated state. At the different densities of the components, fitting a three-state rate equation model, the cross section σ=(3.7±0.9)×10ˉ14 cm2 was obtained for Rb (5D5/2)→Rb(5D3/2) transfer. The cross section for excitation transfer out of the 5Dj doublet are (3.1±1.2)×10ˉ14 cm2 (for j=5/2) and (2.0±0.6)×10ˉ14 cm2 (for j=3/2), respectively. The energy transfer cross section for the Rb (5D)→Rb(7S) is small, (1.6±0.4)×10ˉ16 cm2. The 5Dj state is quenched mainly in the reverse energy pooling processes, i.e. Rb(5Dj)+Rb(5S)→Rb(5P)+ Rb(5P).