The physical properties of the family of cyclotetravanadates A2 M (VO3) 4, where A=Na,Ag and M=Ca,Sr, have been studied by means of x-ray powder diffraction, neutron diffraction, electron diffraction, infrared, Raman, NMR, photoexcitation and pulse cathode beam excitation, and x-ray photoelectron spectroscopies, and band structure calculations. The differences between the structural, vibrational, luminescence, and electronic properties of the alkali metal-containing [Na2 Ca (VO3) 4 and Na2 Sr (VO3) 4] and the d metal-containing cyclotetravanadates [Ag2 Ca (VO3) 4 and Ag2 Sr (VO3) 4] are analyzed. Na2 Ca (VO3) 4, Ag2 Ca (VO3) 4, Na2 Sr (VO3) 4, and Ag2 Sr (VO3) 4 have tetragonal structures, P4/nbm, with a=10.43849 (6), 10.44524 (5), 10.63449 (4), and 10.62574 (6), and c=4.93873 (5), 4.96845 (5), 4.96205 (4), and 4.97930 (4) Å, respectively. The main structural feature of A2 M (VO3) 4 is the tetracyclic [V4 O12] units. The hybridized O2p-V3d states of the tetracyclic [V4 O12] units have a dominant influence on the electronic structure of these compounds. The compounds are semiconducting with a local density approximation band gap increasing from 1.85 eV for Ag2 Ca (VO3) 4 to 3.02 eV for Na2 Ca (VO3) 4. The prospects of these compounds as advanced materials for detectors of photon and corpuscular radiation as well as for color correction of light emission sources such as lamp and light emitting diode sources are discussed.