Dispersed fluorescence (DF) and stimulated emission pumping (SEP) experiments have been carried out on the jet-cooled (LiOLi)-Li-7-O-16-Li-7 molecule. Rotationally resolved SEP bands to v(2)(l)(l=0,2) vibrational angular momentum levels show that LiOLi is a linear molecule. The DF experiments have resulted in the measurement of 54 (v(1),v(2)(l),0) levels of the X (1)Sigma(g)(+) ground state, up to 6000 cm(-1). The energy levels determined experimentally are amazingly close to those calculated very recently for a high-level ab initio LiOLi(X (1)Sigma(g)(+)) potential surface. The DF vibrational level energies are analyzed and discussed in terms of a global fit to an 11-term power series. From the SEP experiments, effective rotational constants B-v1,v(2)(l),0 for several of these vibrational levels [including sigma(g)(+)(l=0) and delta(g)(l=2) vibrational angular momentum states for (v(1),v(2)(l)greater than or equal to2(even),v(3)=0) levels] have also been determined. The bond distance R-0 is estimated to be 1.611+/-0.003 A from an extrapolation of B-v1,0,0 values. Finally, the unusual "Li+O-2Li+" ionic bonding and the low omega(2)=112 cm(-1) bending frequency for LiOLi(X (1)Sigma(g)(+)) are briefly discussed.