W6+ dopant on the NaLa(MoO4)(2):Eu3+ solid solution phosphors with various shapes have been synthesized via the hydrothermal method without using any structural modifier and organic solvents. The morphology and luminescence properties of W6+ doped NaLa(MoO4)(2):Eu3+ phosphors are obtained and characterized by SEM and PL/PLE spectra. Both morphology and luminescence properties are considered to manipulate by the mole ratio of W/Mo. By increasing the W6+ amount, particle shapes are changed from rice-shaped particles to spindle shaped, cocoon-shaped, then to layers of octahedron-shaped. Under UV light excitation, all samples show bright red light due to the characteristic 4f-4f transitions of Eu3+. Tungstate and molybdate phosphors have higher luminescence intensity than that of tungstate and molybdate solid solution phosphors.