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The structure, magnetic and magnetotransport properties of La2/3Sr1/3MnO3(LSMO)/0.33(CuO, ZnO, Al2O3) composites were investigated to explore the role of second introduced phase. The microstructural analysis shows two kinds of grain boundaries: LSMO/LSMO and LSMO/second phase/LSMO. Two maximal resistivities appear in LSMO/0.33CuO and LSMO/0.33ZnO composites while the resistivity of LSMO/0.33Al2O3 decreases monotonically with increasing the temperature from 200 K to 400 K. Moreover, the temperature dependence of magnetoresistance(MR) of LSMO/0.33Al2O3 that decreases monotonically with increasing the temperature is different from that of LSMO/0.33CuO and LSMO/0.33ZnO. A developed two-channel model consisting of scattering model and tunneling model was proposed to fit the resistivity-temperature curves of these composites. The role of second introduced phase and the magnetotransport mechanism of these composites were elucidated.