While the need to reduce the impacts of pesticide use on the environment is increasingly acknowledged, the existing data on the use of agricultural chemicals are hardly adequate to support this goal. This study presents a novel, spatially explicit, national-scale baseline analysis of pesticide toxicity hazard (the potential for chemicals to do harm). The results show an uneven contribution of land uses and growing regions toward the national aggregate toxicity hazard. A hectare of horticultural crops generates on average ten times more aquatic ecotoxicity hazard and five times more human toxicity hazard than a hectare of broadacre crops, but the higher yields and incomes in horticulture mean that both sectors are similar in terms of environmental efficiency. Livestock is the sector with the least contribution to overall hazard, even when the indirect hazard associated with feed is considered. Metrics such as pesticide use (kg/ha) or spray frequency (sprays/ha), commonly reported in highly aggregated forms, are not linearly related to toxicity hazard and are therefore less informative in driving reductions in impact. We propose toxicity hazard as a more suitable indicator for real-world risk than quantity of pesticide used, especially because actual risk can often be difficult to quantify. Our results will help broaden the discussion around pathways toward sustainability in the land-use sector and identify targeted priorities for action.