Background: Emergency contraception (EC) or postcoital contraception has the potential to reduce the number of unwanted pregnancies and thus the abortion rate. Tertiary institutions’ students are a unique group with very high social interaction, but by virtue of their level of education, probably forms a group in any community, which should have an overall higher level of awareness and use of available methods of contraception, including that of EC. Aim: The aim of this study was to assess the knowledge and attitude toward EC, and as well to determine the prevalence of emergency contraceptive use among the students of tertiary institutions in Osun State, Nigeria. Subjects and Methods: A cross‑sectional study using the self‑administered structured questionnaire on questions relating to the socio‑demographic characteristics of the students, sexual relations, knowledge of contraception in general and EC, use and determinants of EC use. Results: A total of 384 of the 400 questionnaire were returned of which male respondents were178/384 (46.4%) while the females were 206/384 (53.6%). Two hundred and seven respondents 207/384 (53.9%) were university students, while 177/384 (46.1%) were polytechnic students. Most respondent 142/376 (37.8%) derived knowledge of EC from friends and family life education from school 186/373 (49.9%). More than half of respondents are in sexual relationships, with only 71/384 (18.5%) showing good knowledge of EC. However, use of EC was 106/384 (27.6%). Conclusion: Most tertiary institutions’ students are involved in a sexual relationship, have poor knowledge of EC and use of EC also. Formal family life education, partner approval, and previous use of EC encourage further use. There is a need for carefully designed education programs and promotion of family life education with deliberate awareness on safe sex practices, including EC in existing students’ health enlightenment programs on campuses.