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Optical emission spectra of a laser induced plasma of vanadium pentoxide (V2O5) using a Nd:YAG laser (1064 nm, 10 ns) in the presence and absence of the magnetic field of 0.45 T have been investigated. The effect of the magnetic field (B) on the V2O5 plasma at various laser irradiances ranging from 0.64 GW cm−2 to 2.56 GW cm−2 is investigated while keeping the pressure of environmental gases of Ar and Ne constant at 100 Torr. The magnetic field effect on plasma parameters of V2O5 is also explored at different delay times ranging from 0 μs to 10 μs for both environmental gases of Ar and Ne at the laser irradiance of 1.28 GW cm−2. It is revealed that both the emission intensity and electron temperature of the vanadium pentoxide plasma initially increase with increasing irradiance due to the enhanced energy deposition and mass ablation rate. After achieving a certain maximum, both exhibit a decreasing trend or saturation which is attributable to the plasma shielding effect. However, the electron density shows a decreasing trend with increasing laser irradiance. This trend remains the same for both cases, i.e., in the presence and in the absence of magnetic field and for both background gases of Ar and Ne. However, it is revealed that both the electron temperature and electron density of the V2O5 plasma are significantly enhanced in the presence of the magnetic field for both environments at all laser irradiances and delay times, and more pronounced effects are observed at higher irradiances. The enhancement in plasma parameters is attributed to the confinement as well as Joule heating effects caused by magnetic field employment. The confinement of the plasma is also confirmed by the analytically calculated value of magnetic pressure β, which is smaller than plasma pressure at all irradiances and delay times, and therefore confirms the validity of magnetic confinement of the V2O5 plasma.