Personal Protective Equipment (PPE) is used to reduce exposure when working with chemicals. For pesticides, exposure scenarios comprise mixing and loading (M&L) and application. The exposure prediction model recommended by European regulatory agencies for operator risk assessments—the Agricultural Operator Exposure Model (AOEM) – is based on 48 operator exposure studies involving over 500 professional operators from 10 European countries in typical working situations to assess exposure under realistic field conditions. We used the AOEM data to assess the efficiency of exposure reduction resulting from wearing chemical-resistant nitrile gloves and non-certified working coveralls during M&L (tank and backpack sprayer), applications using groundboom and airblast spraying, and outdoor and indoor (greenhouse) applications using handheld sprayers. All studies indicated consistent and high exposure reduction > 90% for gloves and non-certified coveralls across all investigated scenarios. Exceptions were almost exclusively observed when an operator incorrectly used the PPE. The mean exposure reduction from all operators, including those that used PPE incorrectly, was 95.0% for gloves and 96.4% for polyester/cotton working coveralls during M&L, and 91.1% for gloves and 94.9% for non-certified coveralls during all application scenarios. This analysis confirms the essential role of PPE and non-certified working coveralls in reducing operator exposure to pesticides. Outliers indicate that operators need to be properly trained and adhere to label instructions to apply pesticides according to good agricultural practices.