A new high-entropy alloy (FeCoNiCr)94Al4Ti2Six with excellent high-temperature oxidation resistance at 1100°C has been developed. The inner oxide behavior with Si added is the key factor of its oxidation resistance. The effect of Si content on the types, continuity, spalling resistance, and diffusion inhibition property of the inner oxide layer were revealed. An internal nitridation of Ti phenomenon was observed in this HEA and the preferential formation of TiN was confirmed by DFT calculation. A novel model for the oxidation resistance of high-entropy alloys affected by silicon is proposed.