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In this study, a series of CoCrFeMnNiSix (x = 0, 0.3, 0.6, 0.9) high-entropy alloys (HEAs) were prepared by suspension melting of cold crucible, annealed at 1000 °C, and then quenched at 900 °C. The changes in the microstructure of the HEAs after the addition of Si were analyzed using X-ray diffraction (XRD), metallographic microscope, scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS), and electron backscatter diffraction (EBSD). The hardness, room-temperature friction, and wear behavior, room-temperature compressive properties, and corrosion resistance of the annealed CoCrFeMnNiSix HEAs were also studied. The results show that when the Si content is 0 and 0.3, the annealed CoCrFeMnNiSix HEA exhibits a single face-centered cubic (FCC) structure. As the silicon content increases, a face-centered orthorhombic (FCO) phase appears. At a Si content of 0.9, a hexagonal close-packed (HCP) phase is observed. After heat treatment, the hardness of the CoCrFeMnNiSix HEAs increases continuously with the addition of Si. The HEA with a Si content of 0.9 achieves the highest hardness of 974.8 ± 30.2 HV. The HEA with a Si content of 0.6 reaches the highest compressive strength and yield strength, which are 1990.3 MPa and 1327.5 MPa. When the Si content is 0.9, the HEA shows the smoothest surface after wear, with the best wear resistance, achieving a value of 0.21 mm−1. In the CoCrFeMnNiSix HEAs after 900 °C heat treatment, the HEA with a Si content of 0.6 exhibits the lowest self-corrosion current density of 0.23 µA/cm2 and the highest pitting potential of 157.65 mV, indicating the best corrosion resistance.