By conducting first-principles calculations with van der Waals correction, we investigate the structural, electronic, and magnetic properties of Gr/MnF3(4)/Gr sandwiched structures. The calculated binding energies were within 54–79 meV per carbon atom for the four Gr/MnF3(4)/Gr sandwiched structures tested in our study. This result implies that the MnF3(4) clusters stabilize the AA and AB stacking in the Gr/MnF3(4)/Gr sandwich structures because of the high electronegativity of the clusters. Charge transfer from bilayer graphene to the MnF3(4) clusters is noted to induce effective hole doping in graphene. Spin polarization in the graphene layer is approximately 100% along the majority direction on the position of the Fermi level in the MnF3-doped structures. The band gaps of the spin-up and spin-down branches and the magnetic moments of the C atoms are increased by compression interlayer spacing. The MnF3 clusters affect the electronic and magnetic properties of graphene in the vicinity of the Fermi level; thus, the clusters are highly suitable for use as a dopant in spintronic applications.