The study was conducted to assess the relationship between Library Anxiety (LA), Emotional Intelligence (EI), and academic achievement of post-graduate students of Pondicherry University. T-tests revealed female students are emotionally intelligent than male students. Analysis of variances showed that students studying in any medium of education i.e. English, Hindi or Mother Tongue, tend to be library anxious while getting exposed to the library for the first time. Tests reveal that utilizing the library services rarely i.e., once in a month, is one of the major reasons for library anxiety being persistent in post-graduate students. There exists a positive relationship between emotional intelligence and library anxiety (r(140) = .178, p = .035), which paved way for further regression analysis. Further analysis disclosed that a unit of increase in EI will lead to 0.229 units increase in LA. So in order to know the factors contributing to this unanticipated increase, MANOVA analysis was done for factors. The results seems to be positive on the factors Perception of emotion and managing own emotion on library anxiety. This study distinct its work from published literatures by having contradicting results. The results show the real emotions of students who are emotionally intelligent, still hesitate to use library due to the fear of library i.e. library anxiety. This paper suggests the importance of Information literacy programs, and awareness programs for the students to be emotionally intelligent and anxiety-free.