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Short-term estimates are not suitable for monitoring and comparing fluctuating pesticide use in EU agricultural land. A discriminative and comparable (<i>HI</i>) herbicide index was evaluated to elucidate herbicide use in the 21st century. The <i>HI</i> was 0.66 kg of active substances per hectare of conventional agricultural land across the EU. However, the <i>HI</i> varied between the 27 EU Member States. The highest mean values of <i>HI</i> were observed in Belgium, the Netherlands, Cyprus, Germany, France, and Denmark, with the lowest in Romania, Greece, Bulgaria, and Latvia. The results showed that the distribution of the <i>HI</i> variable was independent of the geographical location of each country, such as from North to South or from West to East in the EU. It seems that country-level agri-environmental parameters ultimately influenced the herbicide use. To assess the causes of this variability, 31 agri-environmental parameters (formatted into indices to be comparable) were investigated, emphasizing the structural characteristics of the agricultural sector in each EU Member State. Using only the significant independent variables (13 out of 31), linear discriminant analysis (LDA) was applied to explore the differentiation potential of EU₂₇ by creating a discrimination model. The assessment of each one variable in the <i>HI</i> could contribute to the reduction in environmental impacts and the faultless implementation of the European agricultural policy in the near future.