A series of Co-AT (attapulgite) catalysts were prepared by wetness impregnation method. Detailed characterization indicated that there indeed exists interaction between Co and the support AT, leading to the formation of spinel of CoAl2O4 and CoFe2O4. Al and Fe species of AT promote the formation of CoFe2O4 spinel with much lower temperature (400 A degrees C). The catalytic behavior was investigated by the liquid-phase solvent-free oxidation of cyclohexane and Co-AT-1 shown better activity than CoFe2O4 and Co3O4, which was likely due to a cooperation effect between CoFe2O4 and Co3O4.