Stable and high-efficiency narrow-band green phosphor is a key component for wide color gamut liquid crystal display (LCD) backlights. In this paper, narrow-band green-emitting Sr3-3xSi13Al3O2N21:3xEu2+ (0.001 ≤ x ≤ 0.09) (Sr-Sialon:Eu2+) phosphor with a full-width at half maximum of 66 nm has been successfully synthesized by using the solid-state reaction method. All the samples are the pure phase with Sr3Si13Al3O2N21-type structure. Their emission band maximum can be tuned from 495 to 523 nm by increasing Eu2+ content. The compound with x = 0.03 possesses the highest luminescence intensity with the peak position around 510 nm. Luminescent thermal stability gets better with Eu2+ concentration decreasing. The integrated intensity of the sample with x = 0.01 at 425 K remains about 80% of the intensity at room temperature. The host referred binding energy (HRBE) and vacuum referred binding energy (VRBE) schemes are constructed to further explain its luminescent thermal quenching mechanism. White light-emitting-diode (w-LED) device using optimized Sr2.91Si13Al3O2N21:0.09Eu2+ phosphor demonstrates its potential application for LCD backlights.