Graphene has a high work function of 4.6 eV, and it can’t be directly used as thermionic emission material. The graphene work function shows a decreasing trend in alkali metal/oxygen (AM/O) co‐adsorption experiment. Anderson‐Newns(AN) model is a classical theoretical model for calculating the work function of adsorption surface. The present study, aiming at AM/O adsorption system, modified and optimized the AN model by redefining the calculation method of adsorption bond length λ, and established the relationship between material work function, thermionic emission performance and surface coverage. Based on the modified model, the influence of work function decline and thermionic emission performance of cesium/oxygen, potassium/oxygen and sodium/oxygen graphene adsorption systems was studied. The results show that the work function of graphene affected by three AM/O adsorbents is basically the same with the increase of coverage, and all of them quickly decrease to the lowest value and then increased slightly. The maximum work function decline are 3.51 eV, 3.30 eV and 2.83 eV, respectively. At 1,000 K, the maximum output current densities are 340 A/cm2, 36 A/cm2 and 0.15 A/cm2, respectively.This article is protected by copyright. All rights reserved.