Background: In order to explore the possible association between chronotype and risk of medication errors and chronotype in Italian midwives, we conducted a web-based survey. The questionnaire comprised three main components: (1) demographic information, previous working experience, actual working schedule; (2) individual chronotype, either calculated by Morningness–Eveningness Questionnaire (MEQ); (3) self-perception of risk of medication error. Results: Midwives (n = 401) responded “yes, at least once” to the question dealing with self-perception of risk of medication error in 48.1% of cases. Cluster analysis showed that perception of risk of medication errors was associated with class of age 31–35 years, shift work schedule, working experience 6–10 years, and Intermediate-type MEQ score. Conclusions: Perception of the risk of medication errors is present in near one out of two midwives in Italy. In particular, younger midwives with lower working experience, engaged in shift work, and belonging to an Intermediate chronotype, seem to be at higher risk of potential medication error. Since early morning hours seem to represent highest risk frame for female healthcare workers, shift work is not always aligned with individual circadian preference. Assessment of chronotype could represent a method to identify healthcare personnel at higher risk of circadian disruption.