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The effects of Al and Fe ion doping in Mn sites was studied for the colossal La0.67Ca0.33MnO3 magnetoresistance material. It was found that when Fe-doping amount x increases, the crystal cell structure has no obvious change,but the crystal cell volume decrease monotonically for Al-doping. Both resistances increase rapidly and the insulator-metal transition temperature moves to lower temperature and decreases linearly with Al-doping. The area for Al-doping is broader than Fe. At small amount of Al-doping, the resistance satisfy metal transport property when T ＜ TIM. The characteristic of the transport behaviour for Al- and Fe-doping can be explained by terminating the double exchange channel of Mn3+-O2--Mn4+.