Net primary productivity (NPP) is a critical component in terrestrial ecosystem carbon cycles. Thus, quantitatively estimating and monitoring the dynamics of NPP have become key aspects for exploring the carbon cycle of terrestrial ecosystems. Anthropogenic activity, such as urbanization, has significant effects on NPP and increases pressure on the natural resources of a specific region. However, to date, although many studies have focused on the relationship between NPP variation and urbanization, they usually ignored any differences at a long-term spatiotemporal variation of urbanization factors, which led to the insufficient understanding of the urbanization-induced impacts on NPP. As a result, this study effectively explored the spatiotemporal variation of NPP from 2001 to 2012 and its corresponding relationship with urbanization, taking the Hubei Province in China as a case study area. To clarify the degree of urbanization, the spatial distribution and temporal variation of population and gross domestic product (GDP) were simulated based on the elevation-adjusted human settlement index and nighttime lights data. The major results showed that high NPP areas were located in those highlands with widespread woodland, in which the NPP value continued to grow during the period. The low NPP areas were mainly distributed in urban areas, and the NPP value had a continued and visible loss. The population and GDP both had a strong correlation with NPP. The significant negative correlation was concentrated in the center of Hubei, with a dense population and developed economy. In order to further realize their complex relationship, the correlation coefficients between the annual NPP and the two factors from 2001 to 2012 were calculated, and the changing trends were investigated. Overall, the findings of this study may provide a reference for studies on the interaction between ecological environment and socioeconomic processes under the background of global rapid urbanization.