Superlubricity is an ideal lubrication state where friction nearly vanishes between contact interfaces. It has become one of the most important research topics and approaches owing to its significance in reducing energy consumption and preventing device failures. As an efficient and universal lubricating principle capable of achieving superlubricity, rolling lubrication has attracted widespread attention in recent years. In this review, the theoretical concept of rolling lubrication and the experimental research progress of spherical/scroll structures are summarized. The review focuses on the possibility of achieving rolling lubrication using spherical/scroll structures (such as spherical fullerenes, carbon nanotubes, and formed and constructed spherical/scroll structures). The challenges in achieving rolling lubrication are summarized, and the possibility of molecular rolling lubrication, as well as its potential applications in superlubrication, are discussed.