This research work deals with application of Markov Chain Model to educational system. It studied the pattern of students’ enrolment and their academic performance in Mathematics Department, faculty of Science, Ekiti State University, Ado – Ekiti. A transition matrix was developed for ten consecutive academic sessions from this transition matrix, we were able to obtain the probabilities of absorption (graduating and withdrawal). Then, the fundamental matrix was obtained to determine the expected length of stay in an academic session and the expected length of stay before graduating. Moreover, two hypotheses were tested; whether the estimated transition matrix is Markovian or not; and whether the estimated transition matrix is stationary or not. It was observed that the estimated transition matrix is Markovian and stationary over the observed periods. Finally, prediction was made on the enrolment and academic performance of students in the Department of Mathematics, Faculty of Science, Ekiti State University, Nigeria .