Farmers’ knowledge and perception of risks associated with pesticides are core issues in adopting sustainable behavior related to pesticides. This study aimed to find out if Romanian farmers’ perceptions regarding the effects of conventional pesticides on pests, health, and the environment can predict farmers’ willingness to replace conventional pesticides with bio ones and to pay a higher price for the latter. This is the first investigation of Romanian farmers’ perceptions regarding pesticides, thus providing information useful both from the market and environmental protection perspectives. Binary logistic regression was performed to test the relationship between the perceived effect of pesticides, on the one side, and willingness to change conventional with bio-pesticides and willingness to pay for bio-pesticides, on the other side. It was found that the efficiency of conventional pesticides on combating pests and their effects on a farmer’s health can predict farmer willingness to replace conventional approaches with bio-pesticides. Conclusions disclose entry points for interventions aimed at improving communication and information strategies at the country level for raising awareness of the adverse effects of pesticide products, both at the food consumer and farmer levels.