A series of Mn 2? -doped and Eu 3? -co-doped calcium molybdato-tungstates, i.e., Ca 1−3x−y Mn y ⌷ x Eu 2x (MoO 4 ) 1−3x (WO 4 ) 3x (0 \ x ≤ 0.2222 when y = 0.0200 and 0 \ y ≤ 0.0667 when x = 0.1667, ⌷ represents vacancy) materials were successfully synthesized via high-temperature annealing. XRD results confirmed the formation of single, tetragonal scheelite-type phases (space group I4 1 /a). A change in both lattice constants (a and c), lattice parameter ratio c/a and progressive deformation of MoO 4 /WO 4 tetrahedra with increasing Eu 3? as well as Mn 2? contents were observed. The melting point of doped materials is lower than the melting point of pure matrix, i.e., CaMoO 4 . New materials exhibit strong absorption in the UV range. They are insulators with the optical direct band gap (E g ) higher than 3.50 eV. The E g values nonlinearly change with increasing dopants concentrations. EPR measurements allowed to establish the nature of magnetic interactions among Mn 2? ions. Additionally, EPR spectra were sensitive on both parameters: Mn 2? and Eu 3? concentration.