A new series of Eu3+ ions-activated calcium gadolinium tungstate [Ca2Gd2W3O14] phosphors were synthesized by conventional solid-state reaction method. The X-ray diffraction patterns of the powder samples indicate that the Eu3+: Ca2Gd2W3O14 phosphors are of tetragonal structure. The prepared phosphors were well characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), Fourier transform infrared spectroscopy (FTIR), photoluminescence (PL), and mechanoluminescence (ML) spectra. PL spectra of Eu3+: Ca2Gd2W3O14 powder phosphors have shown strong red emission at 615 nm (D-5(0) -> F-7(2)) with an excitation wavelength lambda (exci) = 392 nm (F-7(0) -> L-5(6)). The energy transfer from tungstate groups to europium ions has also reported. Mechanoluminescence studies of Eu3+: Ca2Gd2W3O14 phosphors have also been explained systematically.