The association between environmental concern (EC) and proenvironmental behavior is well-established in the literature. However, previous studies are limited to cross-sectional designs, small sample sizes, and limited populations (e.g., college students). Thus, longitudinal studies on large sample sizes are needed to understand the complex associations between EC and proenvironmental behavior, which can provide insights into how EC is related to changes in proenvironmental behavior over time. In addition, education and residence are closely related to both environmental attitudes and behavior. The current study investigated how education and residence moderate the longitudinal association between the EC and proenvironmental behavior of 17,658 participants (42.86% male and 57.14% female) with a mean age of 53.05 ± 16.40 years old from Understanding Society: the UK Household Longitudinal Study (UKHLS). Factor analysis and hierarchical regression were used to analyze the data. The current study, for the first time in the literature, found that education and residence significantly moderate the longitudinal association between EC and proenvironmental behavior. Thus, it is important to consider people’s educational level and residence when trying to improve EC, which can then lead to effective proenvironmental behavior.