Main-group p-block metals are ideally suited for mediating two-electron reactions because they cycle between M-n and Mn+2 redox states, as the one-electron state is thermodynamically unstable. Here, we report the synthesis and structure of an SW corrole and its (SbX2)-X-v (X = Cl, Br) congeners. Sbui sits above the corrole ring, whereas Sbv resides in the corrole centroid. Electrochemistry suggests interconversion between the Sbm and (SbX2)-X-v species. TD-DFT calculations indicate a HOMO > LUMO+2 parentage for excited states in the Soret spectral region that have significant antibonding character with respect to the Sb X fragment. The photochemistry of 2 and 3 in THE is consistent with the computational results, as steady-state photolysis at wavelengths coincident with the Soret absorption of (SbX2)-X-v corrole lead to its clean conversion to the S13111 corrole. This ability to photoactivate the Sb X bond reflects the proclivity of the pnictogens to rely on the Pnilliv couple to drive the two-electron photochemistry of M X bond activation, an essential transformation needed to develop HX-splitting cycles.