Three novel neutral manganese(ii) complexes (TPhPONMe2)2MnBr2, (TPhPOOMe)2MnBr2, and (TPhPOCF3)2MnBr2 have been designed and synthesized based on a functionalized Ph3PO ligand. These structures are clarified by single crystal X-ray diffraction analysis, which reveals that they crystallize in centrosymmetric space groups and feature an isolated mononuclear structure with Mn2+ in a tetrahedral environment. The photoluminescence spectra and emission lifetime decay curves of three manganese(ii) complexes show distinct green emission (λem = 498-512 nm) and phosphorescence lifetime (τ = 362.0-663.0 μs). The results of DFT calculations indicate that the energy levels of (TPhPONMe2)2MnBr2 and (TPhPOOMe)2MnBr2 are higher than that of (TPhPOCF3)2MnBr2 due to the electron-donating effect of the NMe2 or OMe group, which explains the blue-shift of the emission wavelength and the increase of emission lifetime. Furthermore, the prepared neutral manganese(ii) complexes can be used for high-resolution luminescent printing.