The discovery of phosphor with efficient red emission is a crucial step in the development of the white light-emitting diodes (wLEDs). Herein, based on the regulation of the W/Zn ratio, the Eu3+-activated ZnWO4-WO3∙0.5H2O-WO3 multiphase phosphor was designed successfully via the one-step hydrothermal treatment route. The effects of the W/Zn ratio on the phase structure, composition, morphology, luminescence property and lifetime of the obtained samples were systematically and comparatively investigated. The obtained product not only maintains the multi-wavelength excitation feature of ZnWO4:Eu3+ phosphor, but also sharply improves the characteristic emission intensity of Eu3+ ions. It is found that the WO3∙0.5H2O crystal has a special 3D interconnected channel structure, which is a relatively much access to the chemical behavior and permits the ready insertion of part of Eu3+ ions, and this coordination environment can obtain strong pure red light emission. Further, the ZnWO4-WO3:Eu3+ phosphor obtained after dehydration treatment can be excited more efficiently in the deep-ultraviolet (DUV), near-ultraviolet (NUV) and blue light regions, and its quantum efficiencies reach 18%, 22% and 21.2%, respectively. Besides, it also exhibits better CIE chromaticity coordinate, higher color purity than commercial Y2O2S:Eu3+ phosphor. Therefore, the ZnWO4-WO3:Eu3+ is promising for the application in red phosphor with different wavelengths for wLEDs.