Spectroscopic investigations investigations on Mn2+ doped 20ZnO + xLi(2)O + (30-x)Na2O + 50B(2)O(3) (5 <= x <= 25) (ZLNB) glasses reveal the non-linear behavior in their physical and structural properties. FT-IR spectra of ZLNB glasses reveal diborate units in the borate network. EPR spectra exhibit characteristic resonance signals of Mn2+ ions. A well resolved six line hyperfine structure around g = 2.02 corresponds to the sites of Type II, and a weak broad shoulder around g = 2.7 followed by an unresolved intense signal at g = 4.25 corresponding to sites of Type I are observed for their respective transitions. A large value of zero-field splitting parameter (D) is observed and it behaves non-linearly, reaches a maximum at x = 15 mol% with increase in Li2O content. Delta g values reveal the ionic nature of glass systems. Optical absorption spectra suggest the distorted octahedral site symmetry of Mn2+ ions in the host. Mixed alkali effect is evident in bandgap and Urbach energies. (C) 2011 Elsevier Ltd. All rights reserved.