Li2O doped glass-nanocomposites and their crystalline counterparts were developed and analyzed using DC conductivity and cyclic-voltammetic studies. Micro-structural study revealed the distribution of Li10Zn4O9, Li2Zn2(MoO4)3, ZnMoO4, Zn(MoO2)2, Li2Mo6O7, and Li2MoO3 nanophases. Crystalline counterparts exhibited an enhancement in crystallites’ sizes. As the crystalline counterpart was formed by controlled cooling, ZnSeO3 chain structure was expected to break by increasing dimensions of molybdate rod-like structures. Here, crystalline counterpart showed better stability. Interconnected ZnSeO3 nanophases must initiate structural stability as they play a key role in the formation of structure. Li10Zn4O9 and Li2MoO3 nanophases were supposed to be responsible for higher conductivity.