Optical nonlinearities of discrete absorption energy levels of one of the typical heterocyclic aromatic molecules, free-base porphyrins, have been probed over a broad spectral region (400−1600 nm) utilizing intense femtosecond pulses. A wide range of strong one-and multiphoton-induced nonlinear absorptions of both the blue-end Soret (B) band (a u → b 1g ) and red-end orbital mixing split quasi-allowed Q-bands (Q x (0,0; 0,1), Q y (0,0; 0,1), a u → e g ) are critically probed and reported. During the resonant excitation within B-(400 nm) and Q-bands (600−750 nm), the nonlinear absorption has become predominant by the saturation of absorption (SA) of the onephoton absorption (1PA) process due to ground-state bleaching. At nonresonant wavelengths, it is dominated by the reverse saturation of absorption (RSA), involving various nonlinear processes of two-, three-, and four-photon (2PA, 3PA, and 4PA) absorptions, either to B-or Q-bands (1100−1600 nm). The laser intensity-dependent nonresonant (2PA, 800 nm) excitations for the prominent B-band show a distinct cross-over from SA to RSA, contributed by the excited-state absorption (ESA) utilizing a three-photon induced (3PA) process, whereas resonant (1PA, 400 nm) excitation reveals a systematic strong SA process. Both wavelength-and intensity-dependent nonlinear refractive index studies exhibit positive electronic Kerr-based self-focusing effects, with prominent contributions of nonlinear absorption and higher-order effects. The spectrally discrete, highly intense laser probing of individual energy bands and the consequent variety of nonlinearities can be broadly generalized for many free-base porphyrins and metalloporphyrins. The present studies provide a strong foundation and new insight into the broad categories of macrocycles, such as porphyrins and phthalocyanines, for myriad applications in nonlinear optics and bio/optophotonics.