Employing social network sites (SNSs) for academic purposes has been investigated in the literature; however, there is not enough scientific knowledge about university instructors' behavioral perceptions and values that drive their academic use of SNSs. Therefore, a systematic cognitive framework, regarding SNSs academic usage, is beneficial to understand these behavioral perceptions. This research utilizes the means-end chain (MEC) analysis approach to investigate university instructors' cognitive structure toward the academic use of SNSs. It identifies important requirements for the effective academic use of SNSs by recognizing the relationship between the critical features of SNSs and instructors' perceived values derived from these features. The findings show that seven significant features of SNSs form 45 MECs that appear to be the most useful features used by university instructors for academic purposes. These seven features were found to be cognitively associated with 10 positive benefits, which are crucial to the fulfillment of nine of the instructors' personal values. Of the seven features, following others and being a group member were used most frequently by instructors in their academic practices. These two features were of significant value for the instructors to achieve a sense of accomplishment. The findings have practical implications for instructors and educational institution policy makers to enhance the effectiveness of SNSs use in academic settings.