Nonlinear optical properties of tetraphenylporphyrin (H2TPP) and protonated tetraphenylporphyrin (H4TPP2+) in tolu-ene were investigated by Z-scan technique using a nanosecond laser with 5 ns pulse at 532 nm. Results show that H4TPP2+ exhibits weaker nonlinear refraction but enhanced reverse saturable absorption (RSA) and optical limiting performance in comparison with pristine H2TPP. Since no nonlinear scattering is observed in H4TPP2+ under low input fluence, and H4TPP2+ exhibits weaker nonlinear scattering signals than H2TPP under high input fluence, the enhance-ment of RSA and optical limiting performance can be attributed to the larger ratio of excited state absorption cross-section to that of the ground state of H4TPP2+. H4TPP2+ also exhibits superior optical limiting performance, even better than the benchmark RSA material C60.