The 20% concentration Eu3+-based red-emitting phosphor, nano-sized La6MoO12:Eu3+ was prepared by the Pechini method. X-ray diffraction (XRD), thermogravimetric and differential thermal analysis (TG-DTA), scanning electron microscopy (SEM), photoluminescence (PL), and decay curves were used to characterize the resulting samples. The phosphor can be efficiently excited by near UV light and exhibits an intense red luminescence corresponding to the electric dipole transition D-5(0) -> F-7(2) at 615 nm. When the phosphor was mixed into poly(vinyl alcohol) aqueous solution, the fluorescent nanofibers could be prepared by electrospinning process. It was suggested that the La6MoO12:Eu3+ phosphor would be a promising red component for solid-state lighting devices based on InGaN or GaN light-emitting diodes.