The assembly of Mo$^{VI}$O$_2^{2+}$ and methoxy-substituted salicylaldehyde nicotinoyl hydrazone ligands afforded two classes of hybrid polyoxometalates (POMs). In the Class I architectures, [MoO$_2$(HL$^{1-3}$)(D)]$_2$[Mo$_2$O$_{19}$]·xCH$_3$COCH$_3$ (D = CH$_3$COCH$_3$ or H$_2$O, x = 0 or 2, and L$^{1-3}$ = ligands bearing the OMe group at position 3, 4 and 5, respectively), the main driving force for self-assembly is the electrostatic interaction between the components. Class II architectures are composed of a POM anion covalently linked to two Mo-complex units through the terminal O$^t$ or bridging μ$_2$-OPOM oxygen atoms, as found in Lindqvist-based hybrids [{MoO$_2$(HL$^{1-3}$)}$_2$Mo$_6$O$_{19}$]·xCH$_3$CN (x = 0 or 2) and the asymmetrical β-octamolybdate-based hybrid [{Mo$_2$O$_4$(HL$^2$)(H$_2$L)}{MoO$_2$(HL$^2$)}$_2$Mo$_8$O$_{26}$]·CH$_3$CN·H$_2$O. Quantum chemical calculations were applied to evaluate the impact of the POM hybrid constituents on the hybrid-type stability, showing that it strongly depends on the ligand substituent position and ancillary ligand nature. Hybrids were tested as catalysts for cyclooctene epoxidation using tert-butyl hydroperoxide (TBHP in water or decane) and with or without the addition of acetonitrile (CH3CN) as an organic solvent. The catalytic results provided by the use of TBHP in decane are the best ones and classify all the prepared catalysts as very active, with the conversion of cyclooctene >90%, and high selectivity towards epoxide, >80%. We also examined the influence of the ligand structure, POM's hybrid type, and coordination mode on the Mo-hybrid activity and selectivity.