The short bond length of the linear ground state of the (LiOLi)-Li-7-O-16-Li-7 molecule has been accurately determined to be 1.606 +/-0.008 Angstrom by analysis of the rotational structure of several bands assigned to transitions from the jet-cooled (1)Sigma (+) vibronic ground state to a bent B-1(1) excited state. This value is in good agreement with, but more accurate than, other experimental and ab initio bond-length estimates for the prototypical ionically bound triatomic molecule Li+O-2Li+. (C) 2001 American Institute of Physics.