The work is on library instruction programme as a correlate of undergraduate students’ Utilization of Library Materials in Adeyemi College of Education, Ondo, Nigeria. The research design used for this study is ex-post facto research design. The population comprises all the undergraduates in Adeyemi College of Education, Ondo. Simple random and stratified random sampling technique was employed for the study. One hundred and twenty users were sampled from the programme in all the schools (strata) in the college through library access. Out of 120 copies of the questionnaire administered to the students in Adeyemi College of Education, Ondo, 114 (99%) were returned and used for the analysis. The researchers collected the data through face-to-face administration of questionnaire. Five research questions and two hypotheses were used for the study. The data generated were interpreted using percentages and frequencies; mean and standard deviation through Likert scaling of the responses where applicable. Based on this result, the students’ knowledge about the methods of Library Instruction Programmes (LIP) course in Adeyemi College of Education, Ondo are classroom teaching, library orientation, library guide and ask a librarian. It was inferred that the students’ rate of understanding of the Library Instruction Programme topics is high and the rate of students’ use of Library resources in Adeyemi College of Education Library is low. The challenges that students experience during Library Instruction Programme course in Adeyemi College of Education, Ondo are non utilization of ICT for library instruction, inadequate classroom for library instruction, shortage of staff (librarians) to instruct students, lack of interest in library instruction programme among others. The paper concluded that students in Adeyemi College of Education understand some of the concepts of Library Instruction Programme (LIP) without any basis on gender differences. However, the services in the library were under explored. It was therefore recommended that librarians should sensitize the users more on the services provided in the library for optimal satisfaction of the users. And that the challenges of the students in the course LIP should be tackled by the lecturers and college authority for the benefits of getting desired results in the students’ knowledge of the course for maximal utilization of the library resources.