The selective insertion of CO and CO2 into the C-O and O-H bonds of alcohols by the Se-Ru-CO hydride clusters [(mu-H)Ru-4(CO)(10)Se-2](-) (1) and [(mu(3)-H)Rus(CO)(14)Se](-) (2) was demonstrated by a cooperative effect of the protonic hydride, the electron-rich Ru atom, and the electronegative Se atom as well as the symmetry of the clusters. These reactions generated the first examples of Se-containing ruthenium carboxylate and alkylcarbonate clusters [{(mu-H)Ru-4(CO)(10)Se-2}(2){Ru-2(CO)(4)(mu-eta(1)':eta(1)-OOCR)}](3-) (R = Me, 3; Et, 4) and [{(mu-H)-Ru-4(CO)(10)Se-2}(2){Ru-2(CO)(4)(mu-eta(1):eta(1)-OOCOR)}](3-) (R = Me, 5; Et, 6), respectively. These results disclosed herein provide a new avenue for the capture and storage of CO and CO2 and useful synthetic routes to novel RCOO--and ROCOO--bridged ruthenium selenide clusters.