This paper takes the population structure and industrial structure of Henan Province as the main line，takes 18 prefecture-level cities in Henan Province as the research object. By constructing a population structure and industrial structure evaluation index system and using a grey relational model and a coupling degree model to analyze the coupling characteristics of population structure and industrial structure. The results show that the degree of coupling between the two major structures presented “inverted U-shaped” changes from 1998 to 2015，and that they were tended to antagonize and ultimately tend to be coordinated by low-level coupling； the degree of correlation between population structure and industrial structure varies. There is a high degree of association between these two structures，which is a medium-high degree of association. Among them，the proportion of the elderly population，the proportion of middle school students and above and the tertiary industry are relatively high. The proportion of the population below the primary school is the main driving force for the development of the primary industry. The urban population and the working-age population are important factors affecting the development of the secondary industry. Each area in Henan Province can be divided into four types：low-level coupling region，antagonistic coupling region，running-in coupling region，and coordinated coupling region. The spatial distribution of the population-industry coupling degree in the province is dominated by low-level coupling types and antagonistic coupling types. Coarse and coordination regions are mostly concentrated in the central and northwest regions，and low-level coordination regions are generally distributed in the southwest region. The overall distribution shows a stepped distribution state，and the same type of area appears the spatial agglomeration characteristics in space.