Refractory high-entropy alloys are considered as potential structural materials for elevated temperature applications. To obtain refractory high-entropy alloys with high strength, different amounts of Si were added into the NbMoTiVW refractory high-entropy alloys. The effects of Si on the phase constitution, microstructure characteristics and mechanical properties of NbMoTiVWSix alloys were investigated. Results show that when the addition of Si is 0, 0.025 and 0.05 (molar ratio), the alloys are consisted of primary BCC and secondary BCC in the intergranular area. When the addition of Si is increased to 0.075 and 0.1, eutectic structure including silicide phase and secondary BCC phase is formed. The primary BCC phase shows dendritic morphology, and is refined by adding Si. The volume fraction of intergranular area is increased from 12.22% to 18.13% when the addition of Si increases from 0 to 0.1. The ultimate compressive strength of the NbMoTiVW alloy is improved from 2,242 MPa to 2,532 MPa. Its yield strength is also improved by the addition of Si, and the yield strength of NbMoTiVWSi0.1 reaches maximum of 2,298 MPa. However, the fracture strain of the alloy is decreased from 15.31% to 12.02%. The fracture mechanism of the alloys is changed from mixed fracture of ductile and quasi-cleavage to cleavage fracture with increasing of Si. The strengthening of alloys is attributed to the refinement of primary BCC phase, volume fraction increment of secondary BCC phase, and formation of eutectic structure by addition of Si.