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Single phase Ba3A(V2O7)2 (A = Mg, Zn) ceramics were prepared through a conventional solid‐state ceramic route. The structural and microwave dielectric properties of Ba3A(V2O7)2 (A = Mg, Zn) compositions have been investigated. Powder X‐ray diffraction and Raman spectroscopic studies have been carried out to confirm the phase purity and crystal structure of prepared Ba3A(V2O7)2 (A = Mg, Zn) compositions. Scanning electron microscopic images for Ba3A(V2O7)2 (A = Mg, Zn) ceramics exhibit a homogeneous and dense microstructure. The microwave dielectric properties of the samples were studied using Hakki–Coleman post resonator and cavity perturbation methods. Ba3Mg(V2O7)2 ceramic has a dielectric constant (εr) of 10.3, quality factor (Q x f ) of 43400 GHz and temperature coefficient of resonant frequency (τf) of –46.87 ppm/°C at 660 °C for 1 h. Ba3Zn(V2O7)2 shows a dielectric constant of 10.8, quality factor of 46400 GHz and temperature coefficient of resonant frequency of –78.1 ppm/°C at 660 °C for 1 h. Ba3A(V2O7)2 (A = Mg, Zn) ceramics show excellent chemical compatibility with Al metal electrodes.