The temperature dependence of resistance and magnetoresistance at 77 K for Cu-doped La 2/3Ca 1/3Mn 1-xCu xO-3 have been investigated. Besides the transition similar to the Cu-free sample at ~260 K, a new transition at lower temperature appears for Cu-doped samples. The new transition moves toward low temperature with increasing of Cu content. A new conductive proceeding related to Cu ion may exist. Magnetoresistance at liquid nitrogen shows that MR increased three orders when x is changed from 0 to 0 15. Moreover, the main variation of magnetoresistance is below the field of 1 T.