The development of highly active catalysts for the pyrolysis of ammonium perchlorate (AP) is of considerable importance for AP-based composite solid propellant. In the present study, we produced porous MgFe2O4 architectures by using a facile two-step strategy. A rod-like precursor of MgFe2(C2O4)3⋅nH2O (diameter: 0.5–2.5μm; length: 2–15μm) was fabricated under solvothermal conditions using metal sulfates as raw materials and oxalic acid as the precipitant. Subsequently, porous MgFe2O4 architectures were obtained by the thermal treatment of the as-prepared oxalate precursor, during which the mesopores were formed in situ via the liberation of volatile gases, while the rod-like morphology was well preserved. The catalytic performances of the as-synthesized porous rod-like MgFe2O4 architectures with respect to the AP pyrolysis were assessed using differential scanning calorimetry (DSC) techniques. The results indicated that the high thermal decomposition temperature and the apparent activation energy of AP with 2wt.% MgFe2O4 addition decreased from 445.4∘C to 386.7∘C and from 280.5±11.8 to 147.6±4.8kJ mol−1, respectively. Meanwhile, the decomposition heat of AP with MgFe2O4 as the additive reached up to 1230.6J g−1, which was considerably higher than that of its neat counterpart (695.8J g−1). Thus, porous rod-like MgFe2O4 architectures could be served as the catalyst for the AP pyrolysis.