The (2p+2p) 2 (3) Pi(g) and (2s+3p) 3 (3) Pi(g) states of Li-7(2) have been studied both experimentally and theoretically. Vibrational levels upsilon=0-41 of the 2 (3) Pi(g) state and upsilon=6-10 of the 3 (3) Pi(g) state have been observed by perturbation facilitated optical-optical double resonance (PFOODR) spectroscopy. Our ab initio calculations show that the 2 (3) Pi(g) state, although dissociating into 2p+2p atomic limit, is a Rydberg state and strongly mixed with the (2s+3p) 3 (3) Pi(g) and (2s+3d) 4 (3) Pi(g) Rydberg states. Our theoretical calculations show good agreement with our experimental results.