In order to quantify the core competency of air traffic controllers (ATCO) in multi-post mode, and analyze the ATCO competency-post fit (CPF) degree, this paper proposes the AFE-TOPSIS evaluation method based on the analytic hierarchy process (AHP), factor analysis (FA), and entropy weight method (EWM). Through the analysis of job tasks, it preliminarily develops an evaluation index library of ATCO core competency. Then, it constructs an improved adaptive multi-dimension core competency model divided into four types of post modes. It proposes a method for determining the combined weight of core competency indexes, where the weights are determined subjectively through AHP, combined with the objective method of FA and EWM. Furthermore, it constructs a comprehensive evaluation model based on AFE-TOPSIS and analyzes the CPF degree by calculating the relative closeness degree of each evaluation index. The empirical analysis results show that the four types of core competency models in General, TWR, APP, and ACC post mode include seven dimensions, such as situation awareness, and workload management, which are also graded into the pyramid hierarchical structure of basic, advanced, and high-level. The calculation of the ATCO CPF degree based on the proposed AFE-TOPSIS method can scientifically assist in the fit of ATCO and multi-post mode.