A series of Dy3+-doped Gd10V2O20 phosphors were successfully prepared by the solid-state reaction method. Luminescence properties including the energy transfer process between vanadate group VO43- and Dy3+ were investigated. The Gd10V2O20:Dy3+ phosphor displays three emission bands at 482, 572 and 663 nm, which are originated from the 4F9/2→6H15/2, 4F9/2→6H13/2 and 4F9/2→6H11/2 transitions of Dy3+. The efficient energy transfer occurs from vanadate group VO43- to Dy3+ ions owing to the overlap between the emission of vanadate group VO43- and the absorption of Dy3+. The luminous color of the phosphor was adjustable from blue to yellow region by increasing the concentration of Dy3+. The luminescence intensity ratio (R) of the vanadate group to Dy3+ can be used as an optical thermometer with high sensitivity (2.64% K − 1) in a low-temperature range (130 K), suggesting the prepared phosphor have potential applications in white-emitting and optical temperature sensing simultaneously.