β-Ca3(PO4)2 type phosphors Ca9Tb(PO4)7:Mn2+ were fabricated by high temperature solid state reaction. Under 377 nm light excitation, the Ca9Tb(PO4)7 host displays the green emission attributable to the characteristic emission of Tb3+ ions peaking at 488, 542, 586, and 620 nm, respectively. The red broadband emission is observed when Ca9Tb(PO4)7 is doped with Mn2+ ions. The emission is attributed to the energy transfer from Tb3+ to Mn2+ ions; this facilitates the realization of the tunable green–red emission. The energy transfer mechanism from Tb3+ to Mn2+ is defined as quadrupole–quadrupole interaction. Furthermore, the thermal stability of Ca9Tb(PO4)7:Mn2+ samples has been studied, and it can maintain half the emission intensity exceeding 424 K. This demonstrates their potential applications in white light LEDs (w-LEDs).