In this work, W6+ ions doped Bi2MoO6:20%Yb3+, 2%Er3+ samples were successfully synthesized by a facile and modified hydrothermal method. The main morphology of Bi2MoO6 samples were hollow microsphere structure assembled by nanosheets. The particle size was slightly increased as enhancing W6+ ions doping concentration to 5%, then decreased as the doping concentration increased. Besides, doping W6+ ions can increase the band gap of products from 2.65 ​eV to 2.71eV. The upconversion emission intensity of all samples was strongly influenced by the W6+ ions doping concentration. The luminescent intensity enhanced with the doping concentration increasing up to 3%, then decreased when the W6+ ions concentration further increased. Moreover, the intensity of red emission increased by a large margin than that of green-light region. Besides, the lifetime of 4F9/2 states of Er3+ ions for Bi2MoO6:20%Yb3+, 2%Er3+, 3%W6+ (τ655 ​= ​583.64 ​μs) had significant longer lifetime relative to the Bi2MoO6:20%Yb3+, 2%Er3+ (τ655 ​= ​70.29 ​μs). Hollow microsphere structure Bi2MoO6:20%Yb3+, 2%Er3+, x% W6+ samples were successfully synthesized by a facile and modified hydrothermal method. The upconversion emission intensity of all samples was strongly influenced by the W6+ ions doping concentration. Display omitted •W6+ doped Bi2MoO6:20%Yb3+, 2%Er3+ samples were synthesized by hydrothermal method.•The main morphology was hollow microsphere structure assembled by nanosheets.•The particle sizes and band gaps depended on W6+ ions doping concentration.•The upconversion emission intensity obtained the maximum when W6+ ​doping concentration is 3%.