Core-shell MoSi₂@Nb powder was prepared by electrostatic layer self-assembly method. The surfactants SDS (CHSO₄Na) and CTAB (C₁₉H₄₂BrN) were used to modify the surface of the two particles to make them charged, and the Zeta potential of the suspension was tested by the Zeta potentiometer. Scanning electron microscope, transmission electron microscope and energy dispersive spectrometer were used to characterize the phase, morphology, microstructure and element distribution of synthetic materials. The results show that when the SDS concentration is 2 mmol/L, the CTAB concentration is 3mmol/L and the pH value of Nb suspension is 5, the coating effect is better after secondary cladding. NbSi₂ phase is found at the interface between Nb and MoSi₂ after calcination at 200 °C for 2 h in Ar atmosphere, indicating that Nb is highly active and reacts with Si. Core-shell structure is still retained in MoSi₂@Nb material after spark plasma sintering at 1450 °C for 2 h under uniaxial pressure of 40 MPa. However, it is found that Nb reacts strongly with MoSi₂, and most of the Nb phase is reacted. This issue needs to be addressed in subsequent studies. The fracture toughness (K_IC) of MoSi₂@Nb material is significantly improved to 5.75 MPa·m^0.5 compared with that of MoSi₂ material (3.32 MPa·m^0.5).