The hyperfine structure of the b 3 Pi(u), 2 (3) Pi(g), and 3 3 Pi(g) states of Li-7(2) has been studied by continuous wave perturbation facilitated optical-optical double resonance fluorescence excitation spectroscopy. The b 3 Pi(u) state has case b(beta J) coupling scheme. The hyperfine splittings of the two perturbed b (3) Pi(u) v=19, N=10, J=11e, s, F-1 and v=19, N=5, J=4e, a, F-3 levels were resolved and hyperfine constants determined to be +9.90 MHz and -20.94 MHz, respectively. Fermi contact is the main source of the hyperfine interaction and b(F)(b (3) Pi(u))=+107 MHz has been obtained. The coupling schemes of different 2 (3) Pi(g) levels are different : N=4, 6 levels observed from the b (3) Pi(u) v’=19, N’=5, J’=4e, a, F-3 intermediate level and the N=10 levels observed via the b (3) Pi(u) v’=19, N’=10, J’=11e, s, F-1 intermediate level have case b(beta J) coupling; the N=5 levels observed via the b (3) Pi(u) v’=19, N’=5, J’=4e, a, F-3 intermediate level and the N=9, 11 levels observed from the b (3) Pi(u) v’=19, N’=10, J’=11e, s, F-1 intermediate level are closer to case b(beta S) coupling. Hyperfine constants have been calculated and the Fermi contact constant, b(F)(2(3) Pi(g),)=60 MHz is obtained. The 3 (3) Pi(g), State is a Rydberg state and has case b(beta S), coupling with b(F)(3 (3) Pi(g))approximate to 100 MHz.