This work investigates the applicability of multicenter delocalization analysis to the characterization of pericyclic reactions. The results indicate that multicenter delocalization indices are a powerful tool for studying concerted processes, allowing the characterization of aromatic transition states with a significant increase in the electron delocalization. Moreover, an advantage over magnetic-based indices is that multicenter delocalization indices are not influenced by local electron currents but by the electron delocalization along the multiple (n) centers, and provide, in a quantitative sense, more reliable results. A thorough comparison with magnetic-based indices is carried out for the trimerization reaction of acetylene. Tracking the values of multicenter delocalization indices along the reaction path allows investigation of the nature of concerted mechanisms. Six-center electron delocalization displays a maximum at the transition state of the Diels-Alder reaction, whereas a similar maximum of four-center electron delocalization is slightly displaced to butadiene for the ring opening of cyclobutene. The profile of multicenter electron delocalization indices along the reaction path of [2+2] cycloaddition of ketene to ethene shows the presence of the two independent mechanisms that agree with the two HOMO/LUMO orbital interactions previously proposed to dominate this reaction.