LiCaAlN2:Eu3+/Tb3+ red/green phosphors were successfully prepared by conventional solid-state reaction. The photoluminescence (PL) properties and cathodoluminescence (CL) properties of LiCaAlN2:Eu3+/Tb3+ were investigated in detail. The Eu3+ (Tb3+) doped LiCaAlN2 shows red (green) emission peaking at 615nm (550nm). Monitored at 615nm (550nm), it is interesting to found that LiCaAlN2:Eu3+ (LiCaAlN2:Tb3+) has a broad charge transfer transition in the range of 350-450nm (275-375nm) peaking at 380nm (343nm), which can be efficiently excited by n-UV light-emitting diodes (LEDs). Under electron beam excitation, LiCaAlN2:Tb3+ exhibited a good resistance to the current saturation. The white LED has also been fabricated with blue, green, and LiCaAlN2:Eu3+ red phosphor. The results indicate that LiCaAlN2:Eu3+/Tb3+ could be conducive to the development of phosphor-converted LEDs and field emission displays (FEDs).