From the viewpoints of cluster firms’ inner and outer links, and exploitive and explorative learning, the structural and behavioral source of innovative performance is studied in this paper. We divide cluster firms into leading and following firms and study how their establishing these links and their learning behaviors influence their innovative performance to reveal the roles of these links and learning behaviors for innovative performance. We classify and compare 236 chemical industrial cluster firms in Luhe District of Jiangsu Province, using method of SEM. The results firstly show that cluster firms’ inner and outer links are the structural basis of exploitive and explorative learning, and influence innovative performance via exploitive and explorative learning. Secondly, leading firms promote innovative performance via ambidextrous learning, while following firms depend on exploitive learning to promote incremental innovative performance. Thirdly, the path to promote innovative performance are different between leading and following firms, the effective cooperation of which is beneficial to promote cluster innovative performance. The conclusion provides a useful management enlightenment to establish links conducive to cluster innovation, and coordinate learning behaviors and mobilize the role of different types of firms.