This contribution describes the catalytic activity of homobimetallic complexes derived from p-phenylene on the thermal decomposition of ammonium perchlorate (abbreviated as AP). The complexes, [CpFe-p-Ph-FeCp] (1), [Cp*Fe-p-Ph-FeCp] (2), [CpFe-p-Ph'-FeCp] (3) and [Cp*Fe-p-Ph'-FeCp] (4) (with p-Ph: p-Bis(3,4-dimethylcyclopentadienyl)benzene and p-Ph': p-Bis(2,3,4,5-tetramethylcyclopentadienyl)benzene), were compared with the catalytic activity of the catocene (cat) complex previously reported. Furthermore, in order to clarify the mechanism of the bimetallic compounds, it was tested ferrocene (Fe), frequently used as burning rate (BR) catalyst on the thermal decomposition of AP. The synthetized compounds shown a shift on the peak temperature to lower values and an increase in the released heats during thermal decomposition of AP. The burning rate catalytic activity of the compounds on thermal decomposition of AP were examined by thermogravimetry and differential scanning calorimetry techniques. Theoretical calculations of these compounds were carried out to gain further understanding of these catalysts systems.