The structural and spectroscopic characteristics of Mn2+ in LiNaZnP2O5 (LNZP) nanophosphors were prepared by solid state synthesis and investigated. Diffraction of X-rays confirms that the material gets crystallized in orthorhombic phase with Cmcm space group. The average crystallite size for the prepared sample was found to be 28.02 nm and with increase in Mn2+ ions concentration, a systematic decrease in the crystallite size is observed. The microstructure shows that the agglomerated particles consists of irregular shapes for the undoped sample. By increasing the Mn2+concentration, the particles appear as flower-like structure. The EDS pattern showed the elemental compositions of sodium, zinc, phosphor, oxygen and manganese. By using optical absorption spectra, a number of spin-forbidden d-d bands at a range around 390, 420, 465 and 555 nm and corresponding bands were assigned to the transitions 6A1g (S) → 4T2g (D) (390 nm), 6A1g (S) → 4T2g (G) (465 nm), 6A1g (S) → 4T1g (G) (555 nm) and the band observed around 420 nm was assigned to the transition 6A1g (S) → 4A1g (G) + 4Eg (G) which are characteristics of octahedral site symmetry for Mn2+. Electron spin resonance spectra for undoped LNZP (no spectrum) and Mn2+ doped LNZP nanophosphors were analyzed. The crystal field, interelectronic repulsion and spin-Hamiltonian parameters are evaluated and site symmetry of Mn2+ ions is ascribed as octahedral sites having ligands