Bismuth based host materials for doping rare earth ions gained considerable interest due to the possibility of forming crystalline homogeneous solid solution phases over a wide range and their excellent luminescent properties. In the present manuscript, a facile synthesis method for preparation of nanocrystalline NaBi(MoO4)2 and their optical properties are presented. The influence of various synthetic parameters such as precursor concentration, reaction time and reaction temperature on phase formation have been investigated and revealed that these nanoparticles can be synthesized even at 5 °C within 5 min with a Bi/Mo ratio of 1:4. All the doped and undoped samples show scheelite type tetragonal structure. Formation of solid solution between NaBi(MoO4)2 and NaEu(MoO4)2 over the complete range of compositions could be achieved. A systematic decrease in the unit cell parameters is observed with increasing concentration of Eu3+ ion in NaBi1−xEux(MoO4)2. Investigations on the luminescence properties of europium doped samples show excellent red luminescence upon excitation at 465 nm. The quantum efficiency calculated from experimental luminescence studies shows optimum photoluminescence properties in NaBi0.9Eu0.1(MoO4)2 nanoparticles with the highest quantum efficiency of 50%.