We have investigated the role of fused benzo rings on the electronic structures and intramolecular energy relaxation dynamics in a series of benzoporphyrins (Bpl, syn-Bp2, anti-Bp2, Bp3, and Bp4) by using time-resolved fluorescence measurements and theoretical calculations. Interestingly, even though anti- and syn-Bp2 have the same number of fused anti-Bp2 benzo rings, in the respective absorption spectra, shows an obvious splitting of B-x (Q(x)) and B-y (Q(y)) states, whereas syn-Bp2 exhibits degenerate B and Q bands. These features provide two dynamical models for the effect of the position of substituted benzo rings on the intramolecular energy relaxation dynamics. syn-Bp2 gives rise to similar intrarnolecular dynamics from the B state to the Q state in the case of ZnTPP having Do molecular symmetry. On the other hand, anti-Bp2 shows split B and Q bands in the order B-y > B-x > Q(x) > Q(y), which leads a superimposition of the Q(x) (0,0) and Q(y) (1,0) bands. This overlap generates a strong coupling between these two states, which results in a direct internal conversion from B-x (0,0) to Q(y) (0,0). This observation suggests that the anti-type fused position of benzo rings leads to a new mechanism in internal conversion from the B to the Q state. On the basis of this work, further insight was obtained into the effect of fused benzo rings on the photophysical properties of benzoporphyrins, providing a detailed understanding of the structure-property relationship in a series of benzoporphyrins.