Photoluminescence (PL) and crystal structures of the $(l-x)CaWO_4-xLi_2WO_4$ binary system added with $Eu_2O_3$ activator have been characterized. The $CaWO_4;and;Li_2WO_4$ have the scheelite and phenakite structures respectively. The $CaWO_4-Li_2WO_4-Eu_2O_3$ phosphors show the red luminescence of 613 nm peak wavelength. The wavelength range of excitation spectral band is $380~470$ nm with the peak wavelength of 397 nm. The $0.88(0.5CaWO_4-0.5Li_2WO_4)-0.12Eu_2O_3$ showed the most superior luminescence characteristics. The effect of co-doping elements such as $Al_2O_3$ and rare-earth oxides on PL has been characterized. The co-doping elements deteriorated the luminescence intensity except the $Al_2O_3$ and $Gd_2O_3$. The PL characteristics of $CaWO_4-Li_2WO_4-Eu_2O_3$ phosphors have been compared to those of the alkali europium double molybdates (tungstates) of scheelite-related structure such as $LiEu(MoO_4)_2$ and $CsEu(MoO_4)_2$. The crystal structures of $(l-y)[(l-x)CaWO_4-xLi_2WO_4]-yEu_2O_3$ phosphors have been characterized using XRD data and rietveld refinement.