Recently, a new single-phase refractory CrMoNbV high-entropy alloy is predicted, which has not been considered experimentally to date, using the first-principle theory, molecular dynamics, and Monte Carlo simulation methods. As calculated, CrMoNbV alloy should be a stable single-phase BCC crystal structure at high temperatures (above 1,040 K) and decompose at low temperatures. To verify the prediction, this alloy was fabricated to investigate its crystal structure using HEXRD, EBSD, SEM, EDS, and TEM. The experimental results show that CrMoNbV alloy is composed of a single-phase BCC crystal structure, which is consistent with the prediction. Meanwhile, to investigate the decomposition behavior of the alloy, annealed samples are characterized as well, indicating that the decomposition of the alloy does occur. Thus, the experimentally supported calculation method can be used to explore new single-phase high-entropy alloys.