Taking 41 cities in the Yangtze River Delta Region as the research sample, based on the last two national population censuses and the theory of population economy, this paper selects 8 antecedent conditional variables from three dimensions of population natural structure, regional spatial structure and socioeconomic structure. With the methods of fsQCA and NCA, the study explores the population configuration and path to realize urban high green innovation. The results show that a single demographic indicator is not an essential prerequisite of urban high-green innovation. Besides, there are five ways to realize urban high green innovation driven by overall improvement, science and education, technology of urbanization, urban agglomeration and aging. Moreover, scientific research personnel, as the core of all configurations, plays a universal role in promoting urban high green innovation. In the seventh national population census, with the effect of population on urban green innovation greater and the role of aging more obvious, the configuration and path are richer.