Hollow europium-doped yttrium orthovanadate (YVO4:Eu3+) microspheres were fabricated via a sodium dodecyl sulfate (SDS)–polyethylene glycol (PEG)-assisted hydrothermal technique. The as-synthesized hollow YVO4:Eu3+ microspheres were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence spectroscopy (PL). The obtained results showed that the morphology and size of the hollow microspheres have a strong dependence on the hydrothermal reaction time of the YVO4:Eu3+ powders. It is believed that the SDS–PEG clusters perform a function of dual soft-template that results in a unique template-induced secondary assembly in the one-pot synthesis of hollow YVO4:Eu3+ microspheres. The photoluminescence measurement revealed that the YVO4:Eu3+ powders with a spherical hollow shape have better red luminescence compared to the YVO4:Eu3+ solid microspheres. As a result, the controlled synthesis of hollow YVO4:Eu3+ microspheres not only has a great theoretical significance in studying the three-dimensional control and selective synthesis of inorganic materials but also benefits the potential applications based on hollow YVO4:Eu3+ microspheres owing to reducing the usage of expensive rare-earth elements.