While fertilizers have ensured stable and increasing grain production, they have also caused significant environmental pollution problems. Based on a provincial panel data from 2011 to 2021, this study incorporates grain security and environmental pollution into the efficiency measurement system from an efficiency perspective to assess green utilization efficiency of fertilizers (GUEF) in China and to explore its spatio-temporal evolution characteristics and driving factors by the super-efficiency-weighted SBM model, Markov chain model, and bidirectional fixed-effects model. Results indicate that GUEF exhibits a two-stage upward trend and shows significant spatial extensibility. The main grain marketing areas are the primary kinetic regions for its improvement. However, GUEF also suffers from a widening inter-provincial gap and remains relatively low in certain regions. Further analysis reveals that higher income levels among farmers, smaller scales of agricultural production, lower crop damage rates, larger proportions of grain production, and higher levels of socialized services correlate with higher GUEF. Additionally, technological progress is the primary driving force behind the improvement of GUEF, while the contribution of technical efficiency is minimal. Furthermore, excessive fertilizer application remains the main constraint on improving GUEF, while insufficient grain production in certain regions also hinders efficiency improvement. These findings help clarify the spatial and temporal differences and driving factors of GUEF, providing new policy references for safeguarding grain security and promoting green rural development.