A simple efficient method has been proposed to improve the photoluminescence properties of BaAl12O19:Mn2+ green phosphors by the substitution of Si-N bonds for some Al-O bonds in the host crystal. The incorporation of Si-N bonds only led to a reduction in the lattice parameters, but significantly enhanced the photoluminescence intensity both under UV-visible and vacuum UV excitations. These could be ascribed to the relaxation of the spin and parity prohibitions of Mn2+ d-d transitions and the efficient energy transfer from the host lattice to the activator, respectively.