Intense red phosphors, AgGd1−xEux(W1−yMoy)2O8 (x=0.0–1.0, y=0.0–1.0), have been synthesized through traditional solid-state reaction and characterized by X-ray diffraction (XRD) and photoluminescence (PL). XRD results reveal that AgGd1−xEuxW2O8 synthesized at 1000 °C has a tetragonal crystal structure, which is named as high temperature phase (HTP) AgGdW2O8. All phosphors compositions with Eu3+ show red and green emission on excitation either in the charge-transfer or Eu3+ levels. Analysis of the emission spectra with different Eu3+ concentrations reveal that the optimum dopant concentration for Eu3+ is x=0.6 in the HTP AgGd1−xEuxW2O8 (x=0.0–1.0). Studies on the AgGd0.4Eu0.6(W1−yMoy)2O8 (y=0.0–1.0) and AgGd1−xEux(W0.7Mo0.3)2O8 (x=0.0–1.0) show that the emission intensity is maximum for compositions with y=0.3 and x=0.5, respectively, and a decrease in emission intensity is observed for higher y or x values. The Mo6+ and Eu3+ co-doped AgGd(WO4)2 phosphors show higher emission intensity in comparison with the singly Eu3+-doped AgGd(WO4)2 in UV region. The intense emission of the tungstate/molybdate phosphors under 394 and 465 nm excitations, respectively, suggests that these materials are promising candidates as red-emitting phosphors for near-UV/blue GaN-based white LED for white light generation.Research highlights► Tetragonal/monoclinic phases AgGdEuW2O8 are synthesized at different temperatures. ► Luminescent properties of two kinds of structures AgGd1−xEuxW2O8 are discussed. ► Doping of Mo6+ in AgGd1−xEuxW2O8 enhanced luminescent intensities obviously.