As a promising candidate for next-generation aviation structural materials, lightweight refractory high entropy alloys (HEAs) exhibit high strength, low density, and excellent high-temperature performance. In this study, we investigated the influence of local chemical ordering on the properties of Ti–V–Zr–Nb–Al HEAs using Monte Carlo (MC) simulations based on density functional theory (DFT) calculations. We established that the chemical short-range ordering (SRO) in Ti–V–Zr–Nb–Al HEAs increases with the Al content, resulting in a gradual increase in stacking fault energy (SFE). This theoretical investigation suggests that SRO can be utilized to tailor the performance of HEAs, thereby providing guidance for the scientific design of macroscopic mechanical properties.