To expand the applications of low work function materials, high chemical stability is necessary to prevent the surface from unfavorable reactions. We developed a 20-nm-thick lanthanum hexaboride (LaB6) thin film covered by a monolayer hexagonal boron nitride (h-BN), which exhibits not only low work function but also high chemical stability. Results demonstrated that the h-BN/LaB6 heterostructure can be formed by vacuum annealing a nitrogen-doped LaB6 thin film. The formation process was investigated using Auger electron spectroscopy (AES), high-resolution electron energy loss spectroscopy (HREELS), and X-ray absorption near edge structure (XANES) spectroscopy. We have elucidated that the doped nitrogen atoms and boron atoms in the film thermally diffuse into the surface during annealing, thereby forming the monolayer h-BN on the surface. Work function was measured using scanning tunneling microscopy (STM). From a practical perspective, chemical stability was evaluated with a heating temperature necessary for restoring the low work function state after air exposure. The work function was comparable to that of the clean LaB6(100) surface. Moreover, it recovered at a much lower temperature than the cleaning temperature of the LaB6(100) surface. We anticipate that this material development will facilitate implementation of the low work function material.