Based on the panel data of China’s provincial regions and eight economic zones from 2000 to 2021, this paper empirically tests the polarization effect of population aging on labor employment structure. The research show that the aging population promotes an increase in the proportion of primary and high skilled labor force in employment, while reducing the proportion of medium skilled labor force in employment, resulting in an overall “polarized” labor force employment structure, and this adjustment process presents an “inverted U-shaped” feature. From the perspective of eight comprehensive economic zones, the impact of aging in the eastern coastal economic zone on the labor employment structure is consistent and more sensitive to the national sample; The aging population in the southern economic zone promotes the employment of highly skilled labor, presenting a“unidirectional polarization” characteristic, The aging population in the Greater Southwest Economic Zone promotes the employment of low skilled labor force, presenting a “unidirectional polarization” characteristic; The threshold test found that with the increase of per capita income level, there is a clear dual threshold characteristic of the “polarization” effect of aging on labor employment, and it shows a gain effect.