Agriculture is a hazardous occupational industry for farmers and farm workers; therefore, decisions to improve safety in the working place require understanding behavior of farmers and farm workers and factors affecting it. This study examined factors influencing perceived importance of personal safety and safe behavior of farmers in terms of personal protective equipment (PPE) use in pesticide spraying. Data were collected from a previous survey of farmers in rural areas of northern Greece. Over half of the farmers (55.4%) perceived low importance of personal safety in pesticide spraying. Perceived importance of personal safety increased in young farmers, with high education level, and large land area as well as with high perception of risk, knowledge of pesticide toxicity, seminar in pesticide use, access to internet, and perceived usefulness of PPE. Most farmers showed unsafe behavior in PPE use in terms of using long-sleeved shirt, long pants, chemical resistant gloves, socks, and shoes (58.9%). Farmers perceived low risk of pesticides (65.2%), despite the fact that two out of three farmers (66.1%) perceived high usefulness of PPE. Safe behavior in pesticide use increased in young farmers, with high education level, and small land area as well as with high perception of risk, knowledge of pesticide toxicity, seminar in pesticide use, access to internet, and perceived usefulness of PPE. Binary logistic regression analysis showed that knowledge of pesticide toxicity, education, age, and farm size were significant predictors of perceived importance of personal safety. In addition, self-confidence in spraying, following colleagues’ behaviors, risk perception, knowledge of pesticide toxicity, and farm size were significant predictors of safe behavior in terms of PPE use during pesticide spraying. Findings highlight differences in how farmers perceive personal safety and how they finally respond in daily action with respect to personal safety measures. Perception of risk, knowledge of pesticide toxicity, and farm size were common significant predictors for both variables. Lifelong education targeting promotion of knowledge about pesticide risks among farmers should be always a priority.