In this paper, core-shell MoSi₂@Nb powder was successfully prepared by electrostatic layer self-assembly method. Zeta potential of the suspension were tested by Zeta potentiometer. SEM, TEM and EDS were used to characterize the phase, morphology, structure and element distribution of synthetic materials. The results showed that when the SDS concentration was 2mmol/L, the CTAB concentration was 3mmol/L and the pH value of Nb suspension was 5, the coating effect was better after secondary cladding. NbSi₂ phase was found at the interface between Nb and MoSi₂ after calcination at 200℃ for 2h in Ar atmosphere under HRTEM and XRD analysis, indicating that Nb is highly active and reacts with Si. Then, the fact that core-shell structure was still retained in MoSi₂@Nb material after SPS at 1450℃ for 2h with uniaxial pressure 40Mpa under the SEM and EDS analysis. However, XRD results shown that Nb reacted strongly with MoSi₂, and most of the Nb phase was reacted. This issue needs to be addressed in subsequent studies. But, compared MoSi₂ material (K_IC=3.32 MPa?m_0.5⁾, the fracture toughness of MoSi₂@Nb material has been significantly improved to 5.75 MPa?m_0.5^.