This study delves into the intricate relationship between individuals’ environmental knowledge, awareness of the ban on disposable plastic cups, and intentions to separate recyclables. Grounded in the Theory of Planned Behavior, the research design, data collection, and methodology encompassed the acquisition of 483 valid samples from 16 major metropolitan cities and provinces in South Korea. Environmental knowledge was assessed, focusing on two pivotal factors: environmental harmfulness and recycling. Path Analysis, executed through Partial Least Squares Structural Equation Modeling (PLS-SEM), allowed for evaluating path coefficients, specific indirect effects, and total effects of latent variables within the research model. The results illuminate the most influential pathways within the model. Individuals’ attitudes toward separating recyclables substantially impacted their intentions to engage in separation behavior (t = 9.420, R² = 0.380, p < 0.000). Furthermore, environmental knowledge significantly shaped individuals’ attitudes (t = 8.607, R² = 0.271, p < 0.000). Every hypothesis within the model was statistically significant, underscoring the robustness of the findings. An intriguing discovery was that the awareness of the ban on disposable plastic cups exerted a more pronounced influence on individuals’ practical understanding of precise recycling methods, as opposed to their general knowledge about the harmfulness of plastics. In conclusion, this study offers compelling evidence that residents’ environmental knowledge and attitudes toward recycling play pivotal roles in boosting their active participation in waste separation efforts. These findings have substantial implications for environmental policy and awareness campaigns, emphasizing the need to foster knowledge and positive attitudes to promote sustainable recycling practices.