The molecular structure of Ru2(µ-O2CCF3)2(CO)4(NCMe)2, obtained from Ru3(CO)10(NCMe)2 and CF3CO2H, or from Ru3(CO)12 and CF3CO2H in a CH2Cl2/MeCN mixture, is presented. The central Ru–Ru bond [2·683(1) Å] is bridged by the two carboxylato ligands [Ru–O (average) 2·133 Å]. Each ruthenium carries mutually cis CO ligands approximately trans to the Ru–O vectors and an MeCN ligand in the axial position [Ru–N (average) 2·18 Å].