In this work, triboluminescent powders (SrAl2O4: Eu2+, Dy3+) were composited with the typical graphite/epoxy solid lubricant materials, and the corresponding tribological properties and triboluminescent performance were investigated. The results suggest that the introduction of SrAl2O4: Eu2+, Dy3+ could not only maintain the friction coefficient and the wear rate of the graphite/epoxy solid lubricant materials, but also endow the composites intense triboluminescence. Based on the above results, a bilayered SrAl2O4: Eu2+, Dy3+/graphite/epoxy self-lubricating bulk material and a bilayered SrAl2O4: Eu2+, Dy3+/graphite/epoxy solid lubricant coating were developed, and the intelligent wear out early-warning was in situ achieved in the lubricant coating based on the monitoring of triboluminescence.