Enterprise social media is increasingly being recognized as an important technical tool to achieve more effective management and sustainable development. Limited research has been conducted on workplace satisfaction in the enterprise social media context. To fill this gap, we propose a research model explaining how employees’ usage of enterprise social media influences job satisfaction from the social capital perspective. Through a survey of 509 respondents, we conceptualize the constructs of enterprise social media use (i.e., work-related use and social-related use), social capital (i.e., bridging social capital and bonding social capital), and job satisfaction. We empirically validate the proposed model. The results largely support the proposed hypotheses. Firstly, both work-related use and social-related use positively impact bridging and bonding social capital. Secondly, bridging and bonding social capital play different roles in job satisfaction. Bonding social capital promotes job satisfaction, while bridging social capital inhibits job satisfaction. Thirdly, work-related use accumulates more bridging social capital, while social-related use is more conducive to the establishment of bonding social capital. Finally, some theoretical and practical implications are discussed.