Display omitted •Four types of new refractory HEAs are designed.•These HEAs mainly consist of a simple BCC solid solution.•The formation mechanism of β-Ti is proposed.•Oxidation resistance is improved by adding Ti and Si, but reduced by adding V. High-entropy alloys (HEAs) are defined as the alloys composed of at least five principal elements in equimolar or near equimolar ratios, which can facilitate the formation of simple solid solutions during solidification. Recent studies suggested that the refractory HEAs exhibited great promise for high temperature structural materials. However, their oxidation behavior had received little attention. In the present study, Cr, Al and Si elements were added to improve the oxidation resistance, four types of new refractory HEAs were designed and synthesized, including NbCrMoTiAl0.5 (H-Ti), NbCrMoVAl0.5 (H-V), NbCrMoTiVAl0.5 (H-TiV) and NbCrMoTiVAl0.5Si0.3 (H-TiVSi0.3). Their microstructures and oxidation behavior were studied. As expected, these refractory HEAs mainly consist of a simple body-centred cubic (BCC) refractory metal solid solution (RMss) due to the high mixing entropy effect. Solidification process and thermodynamic analysis were investigated to explain the formation mechanism of their microstructures. For all the refractory HEAs, the oxidation kinetics at 1300°C follows a linear behavior. The oxidation resistance of the HEAs is significantly improved with Ti and Si addition, but reduced with V addition.