The sulfonation reaction has been particularly useful to prepare amphiphilic derivatives of 5,10,15-tris(pentafluorophenyl)corrole, but it has been limited to this corrole. We have studied the scope of this reaction, using 5,10,15-triphenylcorrole as the prototypical example of corrole structure. The reaction protocol has been modified to avoid the corrole aggregation, which limited its reactivity in the neat chlorosulfonic acid. Surprisingly, the reaction shows an unprecedented regioselectivity for corrole derivatives, affording 3 as the main product, but also corrole 5, which is the first example of monosubstituted corrole on pyrrole B. By modulating the corrole:chlorosulfonic acid reagent ratio, it has been possible to obtain the antipodal disubstituted product 6, demonstrating again a not usual regioselectivity for corrole substitution. These results allow the preparation of novel amphiphilic corrole derivatives, which open up their potential applications in different fields.