Selective catalytic reduction (SCR) of NO with C3H6 was investigated on porous clay heterostructures modified with CuFe2O4 (CuFe-PCH). The catalysts were characterized by XRD, HRTEM, H2-TPR, XPS, Py-FTIR and in situ DRIFTS technologies. CuFe-PCH showed high SCR activity at low temperature. Among all the catalysts in this study, Cu1Fe-PCH with the molar ratio of Cu:Fe = 1:1 exhibited the best catalytic performance, which reached 58.5% NO removal at 300 °C (0.1%C3H6) and 100% NO removal at 350 °C (0.3%C3H6) respectively. The active components on CuFe-PCH catalyst were mainly CuFe2O4 nanocrystal, exposing (2 2 0) and (3 1 1) planes. The CuFe2O4 species on Cu1Fe-PCH had high crystallinity, good redox ability, large proportion of lattice oxygen, high density of acid sites and strong Brönsted acidity, which were all responsible for the highest C3H6-SCR activity. By in situ DRIFTS, more isocyanates, including Cu-NCO and Fe-NCO, were found on Cu1Fe-PCH, which were beneficial to enhance C3H6-SCR activity. Finally, a possible reaction path was proposed.