Two new bifunctional isolated hybrid compounds, [ε-PMoV8MoVI4O37(OH)3Zn4][iql]4·6H2O (1) and [ε-PMoV8MoVI4O38(OH)2Zn4][bipy]3[(CH3COO)(bipy)2Zn]·2H2O (2) (where iql = isoquinoline and bipy = 2,2'-bipyridine), based on Zn-ε-Keggin were successfully synthesized by self-assembly under hydrothermal conditions. It is interesting to note that acetate in 2 acted as a linker connecting the ε-Keggin anion with the one Zn atom (Zn5) and enabled the ε-Keggin anion to coordinate with more bipy ligands, culminating with a larger isolated system, which is the first reported isolated cluster of Zn5PMo12. Meanwhile, compounds 1-2 show great electrochemical behaviors and excellent electrocatalytic activity for the degradation of NaNO2. In addition, compound 2 displays better third-order NLO performance than 1 due to the presence of more conjugated rings, with a TPA cross section (σ) of 1819 GM, which suggests that compound 2 has the potential to function as a bifunctional material with tremendous prospects.