Using laser induced fluorescence (LIF) and resonance enhanced two-photon ionization (R2PI) spectroscopy, several (ν1′,ν2′,ν3′) vibrational bands of the à 1B1(K′=1)←X̃ 1Σg+(0,0,0) perpendicular transition of the Li167O7Li molecule have been rotationally resolved and analyzed to yield effective A′,B′,C′ values. The estimated geometry of the à 1B1 state does not vary with ν1′ (symmetric stretch mode), but θ′ increases and R′ decreases slightly as ν2′ (bending mode) increases. Extrapolation leads to an estimate for the (0,0,0) state of θ0′=105±5°, R0′=1.86±0.04 Å, and for the potential minimum θe′=102±5°, Re′=1.87±0.04 Å. The strongly bent nature of the à 1B1 state is due to promotion of an O−2 p-electron (b1) from the strongly ionic, linear Li+O−2Li+ ground state to an a1 molecular orbital which has Li/Li bonding character. The à 1B1 state thus has an approximately Li+1/2O−1Li+1/2 charge distribution, so that the ionic bonding is less strong than in the linear ground state, where (from this study and an earlier stimulation-emission pumping study) R0″=1.611±0.003 Å. In fact, the Li–Li distance in the à 1B1 state, ∼3.0 Å, is quite similar to that of the Li2+1 ion, so the bonding may be described as that of Li2+1 bound ionically to the O−1 ion.