This study examines whether structural social capital mediates the association between constant and new Internet use and depressive symptoms among Chinese older adults, and the potential rural/urban differences. This study considered 9642 participants aged over 60 years from the 2016 and 2018 China Longitudinal Aging Social Surveys. Structural equation models were used to examine the mediators of social networks and social participation as latent constructs of structural social capital in the association between constant and new Internet use and depressive symptoms. Constant and new Internet use showed significant total and direct effects on depressive symptoms, but only constant Internet use showed a significant indirect effect on depressive symptoms through structural social capital. The mediating role of social networks was stronger among the urban than rural older adults, and non-volunteering participation mediated the association between the rural Internet users and their depressive symptoms. Therefore, structural social capital mediates the association between Internet use and depressive symptoms among Chinese older adults who are constant Internet users. New Internet users participate less in volunteering activities than non-users, and only join leisure activities to reduce depressive symptoms. The government, information and communications technology industries, health systems, and communities are recommended to increase the perceived ease and usefulness of Internet use, advocate for non-excessive online socializing of new users, and come up with specific policies of Internet use for rural and urban older adults.