We successfully synthesized a verdazyl-based charge-transfer salt [o-MePy-V-(p-Br)2]FeCl4, which has an SV=1/2 on the radical o-MePy-V-(p-Br)2 and an SFe=5/2 on the FeCl4 anion. Ab initio molecular orbital calculations indicate the formation of an SV=1/2 honeycomb lattice composed of three types of exchange interaction with two types of inequivalent site. Further, the SV=1/2 at one site is sandwiched by SFe=5/2 spins through antiferromagnetic (AF) interactions. The magnetic properties indicate that the dominant AF interactions between the SV = 1/2 spins form a gapped singlet state, and the remaining SFe = 5/2 spins cause an AF order. The magnetization curve exhibits a linear increase up to approximately 7 T, and an unconventional 5/6 magnetization plateau appears between 7 T and 40 T. We discuss the differences between the effective interactions associated with the magnetic properties of the present compound and (o-MePy-V)FeCl4. We explain the low-field linear magnetization curve through a mean-field approximation of an SFe = 5/2 spin model. At higher field regions, the 5/6 magnetization plateau and subsequent nonlinear increase are reproduced by the SV = 1/2 AF dimer, in which a particular internal field is applied to one of the spin sites. The ESR resonance signals in the low-temperature and low-field regime are explained by conventional two-sublattice AF resonance modes with easy-axis anisotropy. These results demonstrate that exchange interactions between SV = 1/2 and SFe = 5/2 spins in [o-MePy-V-(p-Br)2]FeCl4 realize unconventional magnetic properties with low-field classical behavior and field-induced quantum behavior.PACS numbers: 75.10.Jm,