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Field electron emission (FE) from an ultrathin multilayer planar cold cathode (UMPC) including a quantum well structure has been both experimentally and theoretically investigated. We found that by tuning the energy levels of UMPC, the FE characteristic can be evidently improved, which is unexplained by conventional FE mechanism. FE emission mechanism, dependent on the quantum structure effect, which supplies a favorable location of electron emission and enhances tunneling ability, has been presented to expound the notable amelioration. An approximate formula, brought forward, can predict the quantum FE enhancement, in which the theoretical prediction is close to the experimental result.