The microstructure and oxidation behavior at high temperatures ranging from 900 °C to 1100 °C of equiatomic CrMoNbTaV high-entropy alloy produced by vacuum arc melting were investigated. The phase component, microstructure, and microhardness of the alloy were examined by using X-ray diffraction, scanning electron microscopy equipped with an energy-dispersive X-ray spectroscope, and Vickers hardness tests, respectively. The as-cast alloy consists of a single body-centered cubic (BCC) refractory metal solid solution due to the high mixing entropy effect and exhibits a dendritic microstructure. The alloy has a very high microhardness value of 923 HV due to the strong solid solution strengthening effect. The average microhardness in interdendrites (950 HV) was higher than that in dendrites (896 HV) because of composition segregation. The oxidation kinetic curves of the alloy after exposure to air at 900 and 1000 °C follow the pseudo-parabolic rate law, while the mass gain increases first and then decreases at 1100 °C. The thickness of the oxide layer increases with the increasing of oxidation time. The long rod-shaped oxidation products are composed of Nb2O5, NbO2, CrTaO4, CrNbO4, Ta9VO25, Nb9VO25, and TaO after oxidation at 900 and 1000 °C for 25 h. The oxides of CrTaO4 and CrNbO4 disappear as the oxidation temperature elevated to 1100 °C.