GdVO4-based dual-mode phosphors were successfully synthesized via a hydrothermal approach. The X-ray diffraction analysis determined the tetragonal structure as well asI41/amdspace group of products by comparing with a reference pattern no. ICDD #01-072-0277. The morphology of yielded phosphors was confirmed by transmission electron microscopy and scanning electron microscopy. Detailed spectroscopy analysis revealed tunable luminescence properties with an increasing Yb3+content in series of GdVO4: x% Yb3+, y% Tm3+, 5% Eu3+(x = 5, 10, 15, 20; y = 0.1, 0.5, 1) phosphors. For Yb3+, Tm3+, and Eu3+- codoped phosphors we observed bands related to the1G4→3H6and1G4→3F4transitions of Tm3+ions, occurred through the cooperative up-conversion mechanism, where two nearby Yb3+ions were involved in near-infrared absorption. Moreover, the GdVO4: 20% Yb3+, 0.5% Tm3+, 5% Eu3+showed the most outstanding color tunability from red color (x = 0.6338, y = 0.3172) under UV to blue color (x = 0.2640, y = 0.1988) under NIR excitation, which can be applied in anti-counterfeiting activity.