Mass media especially television has been a major agent of socialization and education in the society through edutainment programmes like Who Wants to be a Millionaire, Brain Test, Quiz T.V, Debate” and many more. Today, education is not limited within teacher and four wheels of the classroom because television has proved to be a relevant teacher and instructor. Therefore, the research examines the MTN Who Wants to be a Millionaire as tool of socialization among students in tertiary institutions. The study is anchored on three theories which are Perception Theory, Uses and Gratification Theory and The Entertainment-Education Theory. However, for the purpose of this paper, survey research method was employed while questionnaires were administered to 200 respondents who were drawn using a simple random sampling technique of which 190 copies of the questionnaire were completely filled and returned for analysis. The data collected were analysised and interpreted using frequency and percentage tables method with SPSS version 20. It is recommended that television industry should as a matter of fact create many decent educative programmes that will continue to promote the educational values of Nigeria while specialised presenter should be groomed on educational programmes while regular training, seminars and workshops should also be organised for the presenter, this will boost the educational morale of students while they are been entertained as well.