zirconium‐mediated double homologation method was successfully applied for the synthesis of multi‐substitutedpentacenederivatives from 1,2,4,5‐tetrakis(propargyl)benzenes. The bis(zirconacyclopentadiene) intermediates were also characterized. Among these symmetrical derivatives, tetra‐ and octa‐substitutedpentacenes undergo reversible conversion between monomeric and dimeric forms.