In this work, the structural, optoelectronic, nuclear magnetic resonance (NMR) and electric field gradient (EFG) of the pure BiCaVO۵ and substituted by Mg and Cd atoms were studied by the first principle calculation. The generalized gradient approximation (GGA) with including spin–orbit (SO) coupling effects was used to calculate the band gap values. Indirect band gaps values of ۳.۲۷, ۳.۱۸ and ۲.۵۸ eV are calculated for BiMVO۵ (M = Ca, Mg and Cd) compounds by GGA + SO, respectively. T he band gap values decrease by including spin–orbit interaction. The obtained results show that the M ions play a key role on the ۲۰۹Bi and ۵۱ V chemical shifts which confirm the optoelectronic properties. Calculated plasmon energies are ۲۸.۷۶, ۲۲.۸۷ and ۲۲.۴۸ eV for BiMVO۵ (M = Ca, Mg and Cd) compounds, respectively. From the EFG spectra’s analysis, it is found that the dominant binding orbitals of BiMgVO۵ compound are formed along the z direction at Bi sites with −۵۶.۷۶ × ۱۰۲۱ V/m۲. The wide plasmon energy range makes these materials suitable for the high-performance optical devices.