A series of Tb3+, Eu3+, Li+ co-doped SrSiO3 phosphors were prepared by high-temperature solid-phase method. XRD results showed that Tb3+ and Eu3+ successfully entered into the SrSiO3 matrix lattice. A strong energy transfer from Tb3+ to Eu3+ exists in the sample, and the energy transfer efficiency between Tb3+ to Eu3+ is calculated to be 94.7%. The doping of the charge compensator Li+ increased the luminescence intensity of SrSiO3:6%Tb3+, 6%Eu3+, 3%Li+ phosphor at 614 nm by 4.2 times and significantly improved the color purity of this phosphor (Cp=85.9%). By the color coordinate analysis, the phosphor color coordinates are located near (0.615, 0.365), which belongs to the red region. The white LED device with a color temperature of 6479K and a color rendering index of 93.8 was obtained through the LED package test, and its luminous performance was very stable under different current drives.