Facing increasingly severe environmental pollution and resource scarcity, China has accelerated its pace of green and low-carbon transformation. Green technological innovation helps economic development by reducing ecological pollution and lowering resource consumption. As an important factor of production for social development, the labor force plays a very significant role in optimizing the economic development structure of our country and achieving high-quality leapfrog development. This article explores the relationship between the allocation of labor resources and green technology innovation based on the aforementioned practical motivations, from both theoretical mechanisms and empirical perspectives. Using provincial panel data from China between 2000 and 2021, a spatial Durbin model was constructed to empirically test the spatial spillover effects of labor resource allocation on green technology innovation and to draw relevant conclusions. Subsequently, to further investigate the heterogeneous impact of labor resource allocation on green technology innovation, China was divided into three major regions—eastern, central, and western—and empirical model tests were conducted on separate samples. The following conclusions have been drawn: Over time, during the 22 years from 2000 to 2021, China's overall labor resource allocation has shown an overall upward trend; China's green technology innovation capability has significantly improved, but regional development is uneven, with a large gap in development between the eastern, central, and western regions; through the study of the spatial Durbin model on the impact of labor resource allocation efficiency on green technology innovation, the results indicate that labor resource allocation has a significant main effect and spillover effect on green technology innovation, meaning that the improvement in labor resource allocation efficiency will promote the increase in the level of local green technology innovation, while the decline in labor resource allocation efficiency will inhibit the increase in the level of local green technology innovation; the impediment effect of the decline in labor resource allocation efficiency on regional green technology innovation varies significantly across different regions, with the central region being the most prominent, followed by the western region, and then the eastern region. Based on the conclusions, the following suggestions are made: Regions should strengthen cooperation and exchanges to promote the coordinated development of green technology innovation. Eastern provinces and cities with a higher level of green technology innovation should lead the surrounding provinces and cities with weaker development, actively engage in cooperation and exchanges in infrastructure and green technology, and establish a more orderly and open green technology trading market, thereby promoting the coordinated development of green technology innovation between regions; adopt market-oriented approaches to remove barriers to the autonomous and orderly flow of labor factors. Give the market a decisive role in resource allocation, reasonably play the role of the government, promote the rational and orderly flow of capital and labor resources between regions, and improve the efficiency of resource allocation.