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Social networking sites offer various opportunities to express opinions on politics and public affairs and to disseminate information to a large circle of acquaintances. The present study aimed to investigate these emerging processes of opinion dissemination based on the classic concept of opinion leadership. In an online survey (N = 527), we assessed activities of posting public or private messages on political and societal topics as well as users’ motivations and personality traits. Personality strength and political interest predicted Facebook opinion leadership, while extraversion was not related to online behavior. With regard to motivational aspects, users primarily aim to distribute relevant information and raise awareness of specific topics. Posting public messages on politics, however, also serves self-presentational goals. Implications of the classic opinion leadership concept for explaining processes of opinion expression in Web 2.0 and differences to offline opinion leaders are discussed.