Stimulated Raman scattering of benzene is studied in liquid-core fiber. Owing to fluorescence and third-order nonlinear 4-sulfphenyl porphyin, the high-order stimulated Raman scattering, such as sixth-order Stokes line of benzene, can be observed at a relatively low input-laser power. The threshold of high Stokes line is lowered with the addition of the 4-sulfphenyl porphyin when the concentration of solution is within 10-6 and 10-9 mol/L. At the same time, the Stokes line width becomes narrow with Stokes line order increasing. These results are expected to be applied to tunable laser, seeding laser, biological molecular structures and biological molecule used in none biological area.