Red phosphor nanoparticles YVO₄:Eu³⁺,Bi³⁺ have been successfully prepared via a facile hydrothermal method with Y₂O₃, Eu₂O₃, HNO₃, Bi(NO₃)₃·H₂O, NH₄VO₃, NH₃·H₂O, HNO₃, EtOH and diethylene glycol (DEG) as raw materials and polyvinyl pyrrolidone (PVP) as accessory ingredient. The as-prepared products were characterized by XRD, SEM, IR and PL. The results show that, all the samples are well crystallized and assigned to be the tetragonal crystal structure as the YVO₄ phase. Their microstructure varied with the pH value of solutions. The YVO₄:Eu³⁺, Bi³⁺ nanoparticles exhibit simultaneously orange (at 594 nm) and red (at 619 nm) emissions. The broad orange-red emissions can be attributed to the ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transition of Eu³⁺ ion in YVO₄ matrix. As the ratio of Eu³⁺/Bi³⁺ increases, the fluorescence intensities increase first and then weaken, while reach the strongest red emission at n_Eu³⁺/n_Bi³⁺=5. Besides, the pH value presents influence on the intensities of the YVO₄:Eu³⁺, Bi³⁺ nanoparticles to some extent. The YVO₄:Eu³⁺, Bi³⁺ nanoparticles prepared in the solution with pH = 10 exhibits the strongest red emission. Finally, the mechanism related with the Bi³⁺→Eu³⁺ energy transfer in YVO₄:Eu³⁺, Bi³⁺ nanoparticles was also discussed.