Uniform Eu-doped NaGd(WO4)2 nanophosphors with a spherical shape have been synthesized for the first time by using a wet chemistry method based on a homogeneous precipitation process at low temperature (120 °C) in ethylene glycol/water mixtures. The obtained nanoparticles crystallized into the tetragonal structure and presented polycrystalline character. The europium content in such phosphors has been optimized through the analysis of the luminescence dynamics (lifetime measurements). By coating the Eu3+-doped wolframate based nanoparticles with fluorescein through a layer-by-layer (LbL) approach, a wide range (4-10) ratiometric pH-sensitive sensor has been developed, which uses the pH insensitive emission of Eu3+ as a reference.