|Developing approaches to effectively control the charge and magnetic states is critical to the use of magnetic nanostructures in quantum information devices but is still challenging. Here we suggest that the magnetic and charge states of transition-metal (TM) doped single-layer boron-nitride (SLBN) systems can be easily controlled by the (internal) defect engineering and (external) electric fields (Eext). The relative positions and symmetries of the in-gap levels induced by defect engineering and the TM d-orbital energy levels effectively determine the charge states and magnetic properties of the TM/SLBN system. Remarkably, the application of an Eext can easily control the size of the crystal field splitting of the TM d orbitals and thus, leading to the spin crossover in TM/SLBN, which could be used as Eext-driven nonvolatile memory devices. Our conclusion obtained from TM/SLBN is valid generally in other TM adsorbed layered semiconductors.